TWI490227B - Antimony compounds useful for deposition of antimony-containing materials - Google Patents

Antimony compounds useful for deposition of antimony-containing materials Download PDF

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TWI490227B
TWI490227B TW098114651A TW98114651A TWI490227B TW I490227 B TWI490227 B TW I490227B TW 098114651 A TW098114651 A TW 098114651A TW 98114651 A TW98114651 A TW 98114651A TW I490227 B TWI490227 B TW I490227B
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precursor
ruthenium
substrate
group
vapor
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TW201004970A (en
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Tianniu Chen
Hunks William
Philip S H Chen
Chongying Xu
Leah Maylott
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Advanced Tech Materials
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/65—Metal complexes of amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/90—Antimony compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/90—Antimony compounds
    • C07F9/902—Compounds without antimony-carbon linkages
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of the switching material, e.g. layer deposition
    • H10N70/023—Formation of the switching material, e.g. layer deposition by chemical vapor deposition, e.g. MOCVD, ALD
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
    • H10N70/8828—Tellurides, e.g. GeSbTe

Description

適於沉積含銻材料之銻化合物Suitable for depositing antimony compounds containing antimony materials 【交互參照之相關申請案】[Reciprocal Reference Related Applications]

本申請案主張美國專利臨時申請案號61/050,111、西元2008年5月2日申請之申請案的權益和優先權。前述申請案的內容一併引用於此供作參考。This application claims the benefit and priority of the U.S. Patent Application Serial No. 61/050,111, filed on May 2, 2008. The contents of the aforementioned application are hereby incorporated by reference.

本發明是關於用來沉積含銻膜至如晶圓或其他微電子裝置基材之基材上的前驅物，及關於製造與使用此種前驅物的方法和前驅物源封裝件(source package)。The present invention relates to precursors for depositing a ruthenium containing film onto a substrate such as a wafer or other microelectronic device substrate, and methods and precursor source packages for making and using such precursors. .

在製造微電子裝置中，近來積極將鍺銻碲硫屬(Ge2 Sb2 Te5 chalcogenide)薄膜沉積用於非揮發性相變記憶體(PCM)，此乃因為其極易與矽基(based)積體電路整合。化學氣相沉積(CVD)和原子層沉積(ALD)處理材料為最常用於先進裝置應用的沉積技術。In the manufacture of microelectronic devices, the deposition of Ge 2 Sb 2 Te 5 chalcogenide film for non-volatile phase change memory (PCM) has recently been actively carried out because of its excellent ) Integrated circuit integration. Chemical vapor deposition (CVD) and atomic layer deposition (ALD) materials are the most commonly used deposition techniques for advanced plant applications.

為符合高深寬比幾何形狀在PCM中之預期應用和達成適當相位與非隔離特性的相應需求，需要在低溫(<400℃)下能有效形成高品質含銻膜的製程。適合之銻前驅物需相容於這些需求，且較佳在標準溫度和壓力下具高揮發性。In order to meet the expected application of high aspect ratio geometry in PCM and the corresponding requirements for achieving proper phase and non-isolation characteristics, a high quality ruthenium containing process is required at low temperatures (<400 ° C). Suitable precursors are compatible with these needs and are preferably highly volatile at standard temperatures and pressures.

本發明是關於用來沉積含銻膜至如晶圓或其他微電子裝置基材之基材上的銻前驅物，及關於製造與使用此前驅物的方法和前驅物源封裝件。This invention relates to tantalum precursors for depositing tantalum containing films onto substrates such as wafers or other microelectronic device substrates, and methods and precursor source packages for making and using precursors.

在一態樣中，本發明是關於銻前驅物，其選自以下分類：In one aspect, the invention is directed to a ruthenium precursor selected from the following classifications:

其中： among them:

R、R1 、R2 、R3 、R4 、R5 、R6 、R7 、R8 和R9 彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基；X彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基(amidinate)、胍基(guanidinate)、異尿酸鹽(isourate)和環戊二烯基(C5 R5 )；以及n為1-7之整數，例如1-6。R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are the same or different from each other, and are each selected from a hydrogen group (H), a halogen, a C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, An alkoxyalkyl group, an aryloxyalkyl group, an imidoalkyl group and an ethoxyalkyl group; X are the same or different from each other, and are each selected from the group consisting of a hydrogen group (H), a halogen, a C 1 -C 6 alkyl group, a C 1 - C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxyalkyl, aryloxy An alkyl group, an imine alkyl group, an ethoxyalkyl group, an amidinate, a guanidinate, an isourate, and a cyclopentadienyl group (C 5 R 5 ); and n is 1-7 An integer, such as 1-6.

依這些通式表示的特殊化合物包括：Specific compounds expressed by these formulas include:

含銻前驅物可包括在一組成物內，該組成物包含：含銻前驅物和溶解化合物的溶劑介質。The ruthenium containing precursor can be included in a composition comprising: a solvent medium comprising a ruthenium precursor and a dissolved compound.

本發明之另一態樣是關於包含上述含銻前驅物蒸氣的前驅物蒸氣。Another aspect of the invention is directed to a precursor vapor comprising the above-described ruthenium-containing precursor vapor.

含銻前驅物可用來沉積含銻膜至基材上。沉積膜的方法包含揮發含銻前驅物而產生前驅物蒸氣，以及在沉積條件下，使基材接觸前驅物蒸氣而形成含銻膜至基材上。含銻前驅物具上述化學式之一。The ruthenium containing precursor can be used to deposit a ruthenium containing film onto the substrate. The method of depositing a film comprises volatilizing a ruthenium-containing precursor to produce a precursor vapor, and, under deposition conditions, contacting the substrate with a precursor vapor to form a ruthenium-containing film onto the substrate. The ruthenium-containing precursor has one of the above chemical formulas.

本發明之又一態樣是關於封裝前驅物，包含前驅物儲存與蒸氣分配容器，該容器含有具上述化學式的含銻前驅物設置於其內。Still another aspect of the present invention is directed to a package precursor comprising a precursor storage and vapor distribution container having a ruthenium containing precursor having the above chemical formula disposed therein.

含銻前驅物可做為組成基材上之鍺銻碲(GST)膜的銻成分，包括使用包含前驅物之蒸氣，以沉積含銻前驅物和一或多個含鍺與碲前驅物至基材上。The ruthenium-containing precursor can be used as a ruthenium component of a ruthenium (GST) film on a substrate, including the use of a vapor comprising a precursor to deposit a ruthenium-containing precursor and one or more ruthenium and osmium-containing precursors to the base. On the material.

前驅物亦可用來形成相變隨機存取記憶體(PCRAM)裝置，包括形成GST膜於基材上來製造此裝置。形成步驟包含使用包含前驅物之蒸氣來沉積含銻前驅物和含鍺與碲前驅物至基材上。The precursor can also be used to form a phase change random access memory (PCRAM) device, including forming a GST film on a substrate to fabricate the device. The forming step includes depositing a hafnium-containing precursor and a hafnium-containing hafnium precursor onto the substrate using a vapor comprising the precursor.

含銻前驅物可存在於組成物內，該組成物包含：含銻前驅物和溶解化合物的溶劑介質。The ruthenium containing precursor may be present in the composition comprising: a solvent medium comprising a ruthenium precursor and a dissolved compound.

含銻前驅物例如由下述製程製備：The ruthenium-containing precursor is prepared, for example, by the following process:

其中：X為鹵素；M為鋰(Li)、鈉(Na)或鉀(K)；以及R彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基-C(NR2 )(NR3 )R4 、胍基-C(NR2 )(NR3 )NR4 R5 、異尿酸鹽、環戊二烯基(C5 R5 )和胍基(-N=C-(NMe2 )2 )。Wherein: X is a halogen; M is lithium (Li), sodium (Na) or potassium (K); and R are the same or different from each other, and are each selected from the group consisting of hydrogen (H), halogen, C 1 -C 6 alkyl , C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxylated Base, aryloxyalkyl, imidoalkyl, ethoxyalkyl, decyl-C(NR 2 )(NR 3 )R 4 , fluorenyl-C(NR 2 )(NR 3 )NR 4 R 5 , different Urate, cyclopentadienyl (C 5 R 5 ) and sulfhydryl (-N=C-(NMe 2 ) 2 ).

製備化合物時，有利地，或可使用三鹵化銻做為起始物，再形成上述環狀物而於銻上留下單一鹵素。此鹵素與陰離子試劑(如環戊二烯鋰化合物)反應形成預定產物。此反應可以下式表示：In the preparation of the compound, it may be advantageous or possible to use ruthenium trihalide as a starting material to form the above-mentioned ring to leave a single halogen on the ruthenium. This halogen reacts with an anionic reagent such as a lithium cyclopentadienide compound to form a predetermined product. This reaction can be expressed as:

其中：M為鋰(Li)、鈉(Na)或鉀(K)；X為氯(Cl)、溴(Br)或碘(I)；以及R1 、R2 、R3 、R4 彼此為相同或不同，且個別選自氫基(H)、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、胺基烷基、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基。Wherein: M is lithium (Li), sodium (Na) or potassium (K); X is chlorine (Cl), bromine (Br) or iodine (I); and R 1 , R 2 , R 3 , R 4 are each The same or different, and each selected from the group consisting of hydrogen (H), C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl And substituted alkyl, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl and ethinyl.

另一合成方式為在存有鹼的情況下，讓中性二元胺直接與三鹵化銻反應，以依下列反應式清除釋放的鹽酸(HCl)：Another synthetic method is to react the neutral diamine directly with the lanthanum trihalide in the presence of a base to remove the released hydrochloric acid (HCl) according to the following reaction formula:

接著，產生之化合物與環戊二烯陰離子反應形成下式化合物：The resulting compound is then reacted with a cyclopentadiene anion to form a compound of the formula:

其中附接至銻原子的R’基團為環戊二烯部分(moiety)，此如下所示：The R' group to which the ruthenium atom is attached is a cyclopentadiene moiety, which is as follows:

其中R1-4 如同上述，且附接至銻(Sb)可構成如下特殊化合物所示之σ-或π-鍵結之錯合物：Wherein R 1-4 is as defined above, and attached to 锑 (Sb) may constitute a sigma- or π-bonded complex represented by the following specific compound:

本發明之再一態樣是關於包含上述銻前驅物蒸氣的前驅物蒸氣。A further aspect of the invention is directed to a precursor vapor comprising the above-described ruthenium precursor vapor.

本發明之另一態樣是關於沉積含銻膜至基材上的方法，包含揮發所述之銻前驅物而產生前驅物蒸氣，以及在沉積條件下，使基材接觸前驅物蒸氣而形成含銻膜至基材上，其中銻前驅物選自以下組成群組：Another aspect of the invention is directed to a method of depositing a ruthenium containing film onto a substrate comprising volatilizing the ruthenium precursor to produce a precursor vapor, and subjecting the substrate to precursor vapor under deposition conditions to form a The ruthenium film is applied to the substrate, wherein the ruthenium precursor is selected from the following group:

其中：R、R1 ﹑R2 ﹑R3 ﹑R4 ﹑R5 、R6 、R7 、R8 和R9 彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基；X彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基、胍基、異尿酸鹽和環戊二烯基(C5 R5 )；以及n為1-7之整數，例如1-6。Wherein: R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are the same or different from each other, and are each selected from the group consisting of hydrogen (H), halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkyl An amine, an alkoxyalkyl group, an aryloxyalkyl group, an imidoalkyl group, and an ethoxyalkyl group; X are the same or different from each other, and are each selected from the group consisting of a hydrogen group (H), a halogen, a C 1 -C 6 alkyl group, and a C group. 1- C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxyalkyl, An aryloxyalkyl group, an imine alkyl group, an ethyl sulfonyl group, a decyl group, a decyl group, an isoturate salt, and a cyclopentadienyl group (C 5 R 5 ); and n is an integer of 1 to 7, such as 1-6 .

本發明之又一態樣是關於封裝前驅物，其包含前驅物儲存與蒸氣分配容器，該容器中含有上述銻前驅物。Yet another aspect of the invention is directed to a package precursor comprising a precursor storage and vapor dispensing container containing the foregoing ruthenium precursor.

本發明之再一態樣是關於形成GST膜至基材上的方法，包含使用上述銻前驅物蒸氣來沉積銻於基材上。A further aspect of the invention is directed to a method of forming a GST film onto a substrate comprising depositing the ruthenium on the substrate using the ruthenium precursor vapor described above.

在另一態樣中，本發明是關於製造PCRAM裝置的方法，包含形成GST膜於基材上來製造此裝置，其中該形成步驟包含使用選自上述銻前驅物之蒸氣來沉積銻於基材上。In another aspect, the present invention is directed to a method of fabricating a PCRAM device comprising forming a GST film on a substrate to fabricate the device, wherein the forming step comprises depositing a tantalum on the substrate using a vapor selected from the foregoing hafnium precursor. .

前驅物可用來形成GST膜於基材上，包括使用包含前驅物之蒸氣，以沉積一或多個所述含銻前驅物和一或多個含鍺與碲前驅物至基材上。The precursor can be used to form a GST film on the substrate, including the use of a vapor comprising a precursor to deposit one or more of the ruthenium containing precursor and one or more ruthenium and osmium containing precursors onto the substrate.

前驅物亦可用來形成PCRAM裝置，包括形成GST膜於基材上來製造上述裝置。The precursor can also be used to form a PCRAM device, including forming a GST film on a substrate to make the device.

在一態樣中，本發明更關於對抗所述前驅物在氣相沉積製程中預先反應的方法，藉以成膜於基材上，其中所述前驅物易預先反應而不當影響膜。在此態樣中，方法涉及在製程中引入抗預反應劑，該抗預反應劑選自由(i)異質原子(O、N、S)有機路易士(Lewis)鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑所組成之群組。In one aspect, the invention more relates to a method of pre-reacting the precursor in a vapor deposition process whereby a film is formed on a substrate, wherein the precursor is susceptible to pre-reaction and does not affect the film. In this aspect, the method involves introducing an anti-prereactor in the process selected from the group consisting of (i) heteroatoms (O, N, S) organic Lewis base compounds, (ii) free radicals. A group consisting of an inhibitor and (iii) a guanidine-containing reagent.

本發明之另一態樣是關於對抗所述前驅物在氣相沉積製程中預先反應的方法，其中多個進料流流到沉積處而成膜於基材上，其中多個進料流的至少一者包括易預先反應而不當影響膜的前驅物。方法涉及將抗預反應劑引到至少一進料流或供應材料、或引到沉積處，抗預反應劑選自由(i)異質原子(O、N、S)有機Lewis鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑組成之群組。Another aspect of the present invention is directed to a method of pre-reacting a precursor against a precursor in a vapor deposition process, wherein a plurality of feed streams are passed to a deposition site to form a film on a substrate, wherein the plurality of feed streams At least one includes precursors that are susceptible to pre-reaction and do not affect the film. The method involves introducing an anti-prereactor to at least one feed stream or supply material, or to a deposition site, the anti-prereactor selected from (i) a heteroatom (O, N, S) organic Lewis base compound, (ii) A group consisting of a free radical inhibitor and (iii) a ruthenium containing reagent.

本發明之又一態樣是關於組成物，包含所述前驅物和此前驅物的抗預反應劑，抗預反應劑選自由(i)異質原子(O、N、S)有機Lewis鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑組成之群組。Still another aspect of the present invention relates to a composition comprising an anti-prereactant of the precursor and a precursor, the anti-reactant selected from the group consisting of (i) a hetero atom (O, N, S) organic Lewis base compound, (ii) a group of free radical inhibitors and (iii) cerium-containing reagents.

在再一態樣中，本發明是關於對抗所述氣相前驅物在接觸基材以沉積膜成分於其上時產生預先反應的方法。方法涉及在基材接觸氣相前驅物前，先使基材接觸抗預反應劑，抗預反應劑選自由(i)異質原子(O、N、S)有機Lewis鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑組成之群組。In still another aspect, the present invention is directed to a method of combating the pre-reaction of the vapor phase precursor upon contact with a substrate to deposit a film component thereon. The method involves contacting the substrate with an anti-prereactor prior to contacting the substrate with the vapor precursor, the anti-prereaction agent being selected from the group consisting of (i) heteroatomic (O, N, S) organic Lewis base compounds, (ii) free radicals. A group consisting of an inhibitor and (iii) a guanidine-containing reagent.

在另一態樣中，本發明是關於一製程，其引進抗預反應劑來鈍化生長膜表面或減慢沉積速度，然後使用另一前驅物或共反應物(如氫氣(H2 )、氨氣(NH3 )、電漿、水(H2 O)、硫化氫、硒化氫、二取代基碲化物(diorganotelluride)、二取代基硫化物(diorganosulfide)、二取代基硒化物(diorganoselenide)等)再活化。在ALD製程或類ALD製程中，鈍化/減慢後再活化的過程可按另一順序施行及依需求反覆進行多次。抗預反應劑選自由(i)異質原子(O、N、S)有機Lewis鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑組成之群組。In another aspect, the invention relates to a process for introducing an anti-pre-reactant to passivate a surface of a growth film or slow down a deposition rate, and then using another precursor or co-reactant (eg, hydrogen (H 2 ), ammonia) Gas (NH 3 ), plasma, water (H 2 O), hydrogen sulfide, hydrogen selenide, diorganotelluride, diorganosulfide, diorganoselenide, etc. ) Reactivated. In an ALD process or an ALD-like process, the process of activation after deactivation/slowing can be performed in another order and repeated as many times as needed. The anti-reactant is selected from the group consisting of (i) a heteroatom (O, N, S) organic Lewis base compound, (ii) a free radical inhibitor, and (iii) a ruthenium containing reagent.

本發明之又一態樣是關於用以成膜於基材上的氣相沉積製程，包括使基材循環接觸所述至少一在氣相中不預先反應的膜前驅物。製程涉及在膜生長期間，引進抗預反應劑來有效鈍化膜表面或減慢膜前驅物的沉積速度，以及在引進抗預反應劑後，使用不同的膜前驅物來再活化膜。Yet another aspect of the invention is directed to a vapor deposition process for forming a film on a substrate comprising cycling a substrate into the at least one film precursor that is not pre-reacted in the gas phase. The process involves introducing an anti-pre-reactant to effectively passivate the surface of the film or slow down the deposition rate of the film precursor during film growth, and re-activating the film using different film precursors after introduction of the anti-pre-reagent.

本發明之其他態樣、特徵和實施例在參閱說明書和後附申請專利範圍後，將變得更清楚易懂。Other aspects, features and embodiments of the present invention will become more apparent from the description and appended claims.

本發明是關於用於成膜應用的銻前驅物，例如化學氣相沉積和原子層沉積應用，藉以形成對應之含銻膜至基材上，本發明並關於製造與使用此前驅物的方法和前驅物封裝件類型的相關製程。The present invention relates to a ruthenium precursor for film formation applications, such as chemical vapor deposition and atomic layer deposition applications, whereby a corresponding ruthenium containing film is formed onto a substrate, and the present invention relates to a method of making and using a precursor The process associated with the type of precursor package.

在此，「膜」是指厚度小於1000微米的沉積材料層，例如從1000微米往下至原子單層厚度。在不同實施例中，本發明之沉積材料層的膜厚例如小於100微米、10微米或1微米，或落入小於200奈米、100奈米或50奈米的薄膜範圍，其視特殊應用而定。在此，「薄膜」是指厚度小於1微米的材料層。此外，「薄膜」是指沉積至高深寬比之窄溝渠和小於90奈米之通孔結構的材料。As used herein, "film" refers to a layer of deposited material having a thickness of less than 1000 microns, for example from 1000 microns down to a single layer thickness of atoms. In various embodiments, the deposited material layer of the present invention has a film thickness of, for example, less than 100 microns, 10 microns, or 1 micron, or falls within a film range of less than 200 nanometers, 100 nanometers, or 50 nanometers, depending on the particular application. set. Here, "film" means a material layer having a thickness of less than 1 μm. In addition, "film" refers to a material deposited into a narrow trench of high aspect ratio and a via structure of less than 90 nm.

在此，單數冠詞「一」、「此」、「該」等包括複數意涵，除非內文另特別指明。In this context, the singular articles "a", "","

在此提出之碳數範圍，例如C1 -C12 烷基，包括此範圍內的各碳數部分(moiety)，是以涵蓋此範圍內介於中間值的每一碳數和任何中間碳數範圍；更應理解此特定碳數範圍內的子範圍可個別地包含在較小的碳數範圍內，此亦落在本發明之保護範圍內，且本發明尚包括特別排除某一或多個碳數的碳數範圍，故排除特定碳數範圍之上限及/或下限的子範圍亦不脫離本發明。因此，C1 -C12 烷基意為包括甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一基和十二基，並且包括其直鏈與支鏈形式。當理解廣泛應用於取代基部分的碳數範圍，例如C1 -C12 ，在本發明之特定實施例中可進一步限制成落在特定較寬取代基部分範圍內的子範圍。舉例來說，如C1 -C12 烷基之碳數範圍在本發明之特殊實施例將進一步限制成涵蓋如C1 -C4 烷基、C2 -C8 烷基、C2 -C4 烷基、C3 -C5 烷基或其他適合子界的子範圍。The range of carbon numbers proposed herein, for example, C 1 -C 12 alkyl, including the carbon number in this range, is to cover each carbon number and any intermediate carbon number in the range between the intermediate values. Ranges; it is to be understood that sub-ranges within this particular range of carbon numbers may be individually included in a smaller range of carbon numbers, which are also within the scope of the invention, and the invention also includes specifically excluding one or more The range of carbon numbers of carbon numbers does not depart from the present invention without excluding the upper and/or lower limits of the specific carbon number range. Thus, C 1 -C 12 alkyl is meant to include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, decyl, undecyl and dodecyl, and Including its linear and branched forms. When applied widely appreciated substituted moieties carbon number range, e.g. C 1 -C 12, this embodiment can be further restricted to fall within the scope of a particular sub-group substituted with a wide range in a specific portion of the embodiment of the present invention. For example, a range of carbon numbers such as C 1 -C 12 alkyl groups will be further limited in the particular embodiment of the invention to encompass, for example, C 1 -C 4 alkyl, C 2 -C 8 alkyl, C 2 -C 4 alkyl, C 3 -C 5 alkyl or other suitable sub-range of the subrange.

關於提出之各種規格和範例，在特定實施例中，本發明前驅物更具體指明規定或限制排除特殊取代基、官能基、部分或結構。故本發明包含限制性組成，例如組成的Ri 為C1 -C12 烷基，但Rj 為矽烷基時，Ri ≠C4 烷基。With respect to the various specifications and examples presented, in certain embodiments, the precursors of the present invention more specifically specify or limit the exclusion of particular substituents, functional groups, moieties or structures. Therefore, the present invention encompasses a restrictive composition, for example, R i of the composition is a C 1 -C 12 alkyl group, but when R j is a decyl group, R i ≠ C 4 alkyl group.

在一態樣中，本發明是有關用於在製造相變隨機存取記憶體裝置而以低溫(T<400℃)沉積含銻(Sb)膜的含銻前驅物，例如用於形成鍺銻碲(GST)膜(如Ge2 Sb2 Te5 )至基材(如晶圓)上。In one aspect, the present invention relates to a ruthenium-containing precursor for depositing a bismuth-containing (Sb) film at a low temperature (T < 400 ° C) in the fabrication of a phase change random access memory device, for example, for forming germanium. A germanium (GST) film (such as Ge 2 Sb 2 Te 5 ) is applied to a substrate (such as a wafer).

所述含銻前驅物適於利用如原子層沉積(ALD)和化學氣相沉積(CVD)之技術來形成此膜。較佳之前驅物具高揮發性和適合ALD和CVD應用的期望輸送性質。The ruthenium-containing precursor is suitable for forming the film using techniques such as atomic layer deposition (ALD) and chemical vapor deposition (CVD). Preferred precursors have high volatility and desirable transport properties for ALD and CVD applications.

根據本發明之另一態樣，所述含銻前驅物利用如ALD或CVD之氣相沉積製程來形成特性優越的高共形性(conformal)含銻膜。According to another aspect of the present invention, the ruthenium-containing precursor utilizes a vapor deposition process such as ALD or CVD to form a highly conformal ruthenium-containing film having superior properties.

適合上述成膜應用的所述含銻前驅物可依下示反應式輕易形成：The ruthenium-containing precursor suitable for the above film forming application can be easily formed according to the following reaction formula:

合成銻化合物的一般程序General procedure for the synthesis of hydrazine compounds

其中R彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基-C(NR2 )(NR3 )R4 (amidinate-C(NR2 )(NR3 )R4 )、胍基-C(NR2 )(NR3 )NR4 R5 (guanidinate-C(NR2 )(NR3 )NR4 R5 )、異尿酸鹽(isourate)、環戊二烯基(C5 R5 )和胍基(-N=C-(NMe2 )2 )。Wherein R is the same or different from each other, and is each selected from the group consisting of hydrogen (H), halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxyalkyl, aryloxyalkyl, imidoalkyl, ethoxyalkyl, decyl-C (NR 2) (NR 3) R 4 (amidinate-C (NR 2) (NR 3) R 4), guanidino -C (NR 2) (NR 3 ) NR 4 R 5 (guanidinate-C (NR 2) (NR 3 ) NR 4 R 5 ), isourate, cyclopentadienyl (C 5 R 5 ) and fluorenyl (-N=C-(NMe 2 ) 2 ).

製備化合物時，有利地，或可使用三鹵化銻做為起始物，再形成上述環狀物而於銻上留下單一鹵素。此鹵素與陰離子試劑(如環戊二烯鋰化合物)反應而形成期望產物。此反應可採下式表示：In the preparation of the compound, it may be advantageous or possible to use ruthenium trihalide as a starting material to form the above-mentioned ring to leave a single halogen on the ruthenium. This halogen reacts with an anionic reagent such as a lithium cyclopentadienide compound to form the desired product. This reaction can be expressed as follows:

其中：M為鋰(Li)、鈉(Na)或鉀(K)；X為氯(Cl)、溴(Br)或碘(I)；以及R1 、R2 、R3 、R4 彼此為相同或不同，且個別選自氫基(H)、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、胺基烷基、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基。Wherein: M is lithium (Li), sodium (Na) or potassium (K); X is chlorine (Cl), bromine (Br) or iodine (I); and R 1 , R 2 , R 3 , R 4 are each The same or different, and each selected from the group consisting of hydrogen (H), C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl And substituted alkyl, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl and ethinyl.

另一合成方式為在存有鹼的情況下，讓中性二元胺直接與三鹵化銻反應，以依下列反應式清除釋放的鹽酸(HCl)：Another synthetic method is to react the neutral diamine directly with the lanthanum trihalide in the presence of a base to remove the released hydrochloric acid (HCl) according to the following reaction formula:

接著，產生之化合物與環戊二烯陰離子反應形成下式化合物：The resulting compound is then reacted with a cyclopentadiene anion to form a compound of the formula:

其中附接銻原子的R’官能基為環戊二烯部分，此如下所示：The R' functional group to which the deuterium atom is attached is a cyclopentadiene moiety as follows:

所述含銻前驅物可做為CVD/ALD前驅物，以例如藉由液體輸送技術來沉積含銻膜，其中此化合物備於包括適當溶劑介質的組成物內。在特殊應用中，可用溶劑包括烷烴(如己烷、庚烷、辛烷和戊烷)、芳香羥(如苯或甲苯)、和胺(如三乙胺、三級丁胺)，但不以此為限。讓Sb前驅物溶解或懸浮其中的溶劑介質可為單一成分溶劑或多重成分溶劑組成物。The ruthenium containing precursor can be used as a CVD/ALD precursor to deposit a ruthenium containing film, for example by liquid delivery techniques, wherein the compound is prepared in a composition comprising a suitable solvent medium. In special applications, solvents may include alkanes (such as hexane, heptane, octane, and pentane), aromatic hydroxy (such as benzene or toluene), and amines (such as triethylamine, tertiary butylamine), but not This is limited. The solvent medium in which the Sb precursor is dissolved or suspended may be a single component solvent or a multiple component solvent composition.

若前驅物為液態，則可利用ALD/CVD液體輸送技術而以純液態(neat)輸送，其中液體揮發成對應之前驅物蒸氣，然後在適當的氣相沉積條件下接觸基材(含銻膜將形成於該基板上)。If the precursor is in a liquid state, it can be transported in neat with ALD/CVD liquid transport technology, wherein the liquid volatilizes into a corresponding precursor vapor and then contacts the substrate under appropriate vapor deposition conditions (including the tantalum film) Formed on the substrate).

若前驅物為固態，則可先揮發前驅物、再利用任何適合之固體輸送系統輸送，例如ProE-VapTM 固體輸送與蒸發單元，其可購自ATMI公司(位於美國康乃迪克州丹博瑞市)。一或多個前驅物(因本發明包含使用多種不同的Te前驅物)揮發成對應之前驅物蒸氣後，接著接觸晶圓或其他基材而沉積含銻膜於其上。When the precursor is a solid precursor can first volatile, then using any suitable transport of solid delivery systems, e.g. ProE-Vap TM was evaporated and the solid delivery means, which may be commercially available from ATMI, Inc. (Connecticut, United States Danbo Rui city). One or more precursors (as the invention comprises the use of a plurality of different Te precursors) are volatilized into corresponding precursor vapors, followed by contact with a wafer or other substrate to deposit a ruthenium containing film thereon.

在不同實施例中，如熟諳此技藝者所知，Sb前驅物產生之前驅物蒸氣可與載氣或共反應物(co-reactant)氣體混合，以得到期望沉積厚度、生長速度等。In various embodiments, as known to those skilled in the art, the precursor precursor vapor from the Sb precursor can be mixed with a carrier gas or a co-reactant gas to achieve a desired deposition thickness, growth rate, and the like.

在又一態樣中，本發明是關於製備橋接二醯胺銻化合物的新合成途徑。新合成技術克服了先前技術之合成方式面臨的困難和複雜度，例如低產量和生成難以獲得高純度產物的副產物、及因螯合以致形成單體錯合物、而非產生造成高核性錯合物(包括二聚物、寡聚物和多聚物結構)的橋接多重金屬中心。在一特定態樣中，本發明提出雙醯胺銻，其可用於低溫沉積醯胺銻至基材上。In yet another aspect, the invention is directed to a novel synthetic route for the preparation of bridged bismuthamine compounds. The new synthesis technology overcomes the difficulties and complexity faced by prior art synthesis methods, such as low yields and by-products that are difficult to obtain high purity products, and chelation to form monomeric complexes, rather than causing high nuclearity. Bridging multiple metal centers of complexes, including dimers, oligomers, and polymer structures. In a particular aspect, the present invention provides a bisguanamine oxime which can be used to cryogenically deposit amidoxime onto a substrate.

在一些實施例中，含銻前驅物的特徵至少經核磁共振(NMR)光譜和熱分析(熱重分析儀(TGA)與示差掃瞄熱卡計(DSC))檢測為低熔點固體，其顯示前驅物具備良好輸送性質且殘餘量少(<5%)。故此化合物可做為低溫沉積含銻膜的前驅物。In some embodiments, the ruthenium-containing precursor is characterized by at least nuclear magnetic resonance (NMR) spectroscopy and thermal analysis (thermogravimetric analyzer (TGA) and differential scanning calorimeter (DSC)) as low melting solids, which are displayed The precursor has good transport properties with low residuals (<5%). Therefore, the compound can be used as a precursor for depositing a ruthenium film at a low temperature.

因此，本發明提出數種適用於ALD或CVD沉積銻或含銻膜的含銻化合物，以例如製造包含Ge2 Sb2 Te5 膜的GST裝置。Accordingly, the present invention proposes several cerium-containing compounds suitable for ALD or CVD deposition of ruthenium or ruthenium containing films, for example, to fabricate GST devices comprising Ge 2 Sb 2 Te 5 films.

可由以下反應式製造此銻前驅物。This ruthenium precursor can be produced by the following reaction formula.

其中：X為鹵素；M為鋰(Li)、鈉(Na)或鉀(K)；以及R彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基-C(NR2 )(NR3 )R4 、胍基-C(NR2 )(NR3 )NR4 R5 、異尿酸鹽、環戊二烯基(C5 R5 )和胍基(-N=C-(NMe2 )2 )。Wherein: X is a halogen; M is lithium (Li), sodium (Na) or potassium (K); and R are the same or different from each other, and are each selected from the group consisting of hydrogen (H), halogen, C 1 -C 6 alkyl , C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxylated Base, aryloxyalkyl, imidoalkyl, ethoxyalkyl, decyl-C(NR 2 )(NR 3 )R 4 , fluorenyl-C(NR 2 )(NR 3 )NR 4 R 5 , different Urate, cyclopentadienyl (C 5 R 5 ) and sulfhydryl (-N=C-(NMe 2 ) 2 ).

製備化合物時，有利地，或可使用三鹵化銻做為起始物，再形成上述環狀物而於銻上留下單一鹵素。此鹵素與陰離子試劑(如環戊二烯鋰化合物)反應而形成期望產物。此反應可以下式表示：In the preparation of the compound, it may be advantageous or possible to use ruthenium trihalide as a starting material to form the above-mentioned ring to leave a single halogen on the ruthenium. This halogen reacts with an anionic reagent such as a lithium cyclopentadienide compound to form the desired product. This reaction can be expressed as:

其中：M為鋰(Li)、鈉(Na)或鉀(K)；X為氯(Cl)、溴(Br)或碘(I)；以及R1 、R2 、R3 、R4 彼此為相同或不同，且個別選自氫基(H)、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、胺基烷基、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基。Wherein: M is lithium (Li), sodium (Na) or potassium (K); X is chlorine (Cl), bromine (Br) or iodine (I); and R 1 , R 2 , R 3 , R 4 are each The same or different, and each selected from the group consisting of hydrogen (H), C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl And substituted alkyl, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl and ethinyl.

另一合成方式為在存有鹼的情況下，讓中性二元胺直接與三鹵化銻反應，以依下列反應式清除釋放的鹽酸(HCl)：Another synthetic method is to react the neutral diamine directly with the lanthanum trihalide in the presence of a base to remove the released hydrochloric acid (HCl) according to the following reaction formula:

接著，產生之化合物與環戊二烯陰離子反應形成下式化合物：The resulting compound is then reacted with a cyclopentadiene anion to form a compound of the formula:

其中附接至銻原子的R’官能基為環戊二烯部分，此如下所示：The R' functional group to which the ruthenium atom is attached is a cyclopentadiene moiety as follows:

其中R1 -4 如同上述，且附接至銻(Sb)可構成如下特殊化合物所示之σ-或π-鍵錯合物：Wherein R 1 - 4 is as defined above, and attached to oxime (Sb) may constitute a sigma- or π-bond complex as shown by the following specific compounds:

或者，可進行類似合成方式，但二元胺起始物具不同鏈長，以製造不同尺寸的環狀二醯胺銻化合物，其不同於利用類似上述步驟製造的五員環。Alternatively, a similar synthesis can be carried out, but the diamine starting materials have different chain lengths to produce cyclic bisguanamine compounds of different sizes, which are different from the five-membered rings produced using similar steps as described above.

可由以下反應式製造此銻前驅物。This ruthenium precursor can be produced by the following reaction formula.

其中：M為鋰(Li)、鈉(Na)或鉀(K)；X為氯(Cl)、溴(Br)或碘(I)；n為介於1-6之間的整數；以及R彼此為相同或不同，且個別選自氫基(H)、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、胺基烷基、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基和選擇性取代環戊二烯基。Wherein: M is lithium (Li), sodium (Na) or potassium (K); X is chlorine (Cl), bromine (Br) or iodine (I); n is an integer between 1-6; and R They are the same or different from each other, and are each selected from a hydrogen group (H), a C 1 -C 6 alkyl group, a C 1 -C 6 alkoxy group, a C 3 -C 8 cycloalkyl group, a C 6 -C 10 aryl group, Alkyl, substituted alkyl, aminoalkyl, alkoxyalkyl, aryloxyalkyl, imidoalkyl, ethoxyalkyl and optionally substituted cyclopentadienyl.

本實施例也可進行相同的反應變化，以按特性形成環戊二烯類似物，其中選擇性取代環戊二烯陰離子係附接至Sb原子。This example can also be subjected to the same reaction changes to form a cyclopentadiene analog according to the characteristics, wherein the selectively substituted cyclopentadiene anion is attached to the Sb atom.

所述含銻化合物具有高揮發性和低分解溫度，故適用於ALD和CVD應用。The ruthenium containing compound has high volatility and low decomposition temperature and is therefore suitable for ALD and CVD applications.

這些前驅物適合低溫沉積應用，並具備良好的揮發性和輸送性質。若前驅物化合物為液態或為包括適當溶劑介質之組成物，則可以純液體形式輸送之。如上所述，在特殊應用中，可用溶劑包括烷烴(如己烷、庚烷、辛烷和戊烷)、芳香羥(如苯或甲苯)和胺(如三乙胺、三級丁胺)、或其混合物，但不以此為限。These precursors are suitable for low temperature deposition applications and have good volatility and transport properties. If the precursor compound is in a liquid state or is a composition comprising a suitable solvent medium, it can be delivered in pure liquid form. As noted above, in particular applications, solvents may include alkanes (such as hexane, heptane, octane, and pentane), aromatic hydroxy (such as benzene or toluene), and amines (such as triethylamine, tertiary butylamine), Or a mixture thereof, but not limited thereto.

若前驅物為固態，則可先揮發前驅物、再利用任何適合之固體輸送系統輸送，例如ProE-VapTM 固體輸送與蒸發單元，其可購自ATMI公司(位於美國康乃迪克州丹博瑞市)。一或多個前驅物(因本發明包含使用多種不同的Te前驅物)揮發成對應之前驅物蒸氣後，接著接觸晶圓或其他基材而沉積含銻膜於其上，以例如形成GST層。When the precursor is a solid precursor can first volatile, then using any suitable transport of solid delivery systems, e.g. ProE-Vap TM was evaporated and the solid delivery means, which may be commercially available from ATMI, Inc. (Connecticut, United States Danbo Rui city). One or more precursors (since the invention comprises the use of a plurality of different Te precursors) are volatilized into corresponding precursor vapors, followed by contacting a wafer or other substrate to deposit a germanium-containing film thereon, for example to form a GST layer .

在再一態樣中，本發明是關於具氮施體配位基(donor ligand)的銻化合物，用以沉積銻或含銻膜至基材上，做為如GST相變隨機存取記憶體(PCRAM)裝置之用。In still another aspect, the present invention relates to a ruthenium compound having a nitrogen donor ligand for depositing a ruthenium or ruthenium containing film onto a substrate as a GST phase change random access memory. (PCRAM) device.

更特別地，本發明態樣是關於具至少一所述氮基配位基的Sb(III)前驅物。More particularly, aspects of the invention are directed to Sb(III) precursors having at least one of the nitrogen-based ligands.

所述含銻前驅物可結合適當的共反應物而用於以連續式沉積模式(CVD)或脈衝式/原子層沉積模式(ALD)之膜形成製程，以沉積特性優越的膜。The ruthenium-containing precursor can be combined with a suitable co-reactant for a film formation process in a continuous deposition mode (CVD) or a pulsed/atomic layer deposition mode (ALD) to deposit a film having superior properties.

就類金屬(metal-like)膜而言，較佳採取還原大氣(reducing atmosphere)。本發明之前驅物可做為結合諸如氫氣、氫氣(H2 )/電漿、胺、亞胺、肼、矽烷、鍺烷(如GeH4 )、氨氣、烷烴、烯烴和炔烴之還原共反應物的低溫沉積前驅物。就CVD成膜模式而言，較佳使用諸如H2 、NH3 等還原劑；共反應物電漿則可用於數位或ALD模式，其中脈衝序列的共反應物和前驅物可依據揭露內文利用此技藝熟知的一般CVD與ALD技術分離。作用更強的還原劑亦可用於數位或ALD模式，因共反應物可分離而避免發生氣相反應。就ALD及共形覆蓋高深寬比結構而言，前驅物較佳在某一種大氣(如惰性或弱還原/氧化氣體環境)中展現自限行為，並且在另一種大氣(如電漿、強還原/氧化氣體環境)中快速分解以形成期望膜。In the case of a metal-like film, a reducing atmosphere is preferably employed. The precursor of the present invention can be used as a combination of reduction such as hydrogen, hydrogen (H 2 ) / plasma, amine, imine, hydrazine, decane, decane (such as GeH 4 ), ammonia, alkanes, alkenes and alkynes. A low temperature deposition precursor of the reactants. For the CVD film formation mode, a reducing agent such as H 2 or NH 3 is preferably used; the co-reactant plasma can be used in a digital or ALD mode, wherein the co-reactants and precursors of the pulse sequence can be utilized according to the disclosure. The general CVD and ALD techniques well known in the art are separated. More powerful reducing agents can also be used in the digital or ALD mode, since the co-reactants can be separated to avoid gas phase reactions. In the case of ALD and conformal coverage of high aspect ratio structures, the precursors preferably exhibit self-limiting behavior in one atmosphere (eg, inert or weakly reduced/oxidized gas environments) and in another atmosphere (eg, plasma, strong reduction) Rapid decomposition in / oxidizing gas environment to form the desired film.

使用抗預反應劑(Pre-Reaction-Combating Agent)來形成硫屬膜Use a Pre-Reaction-Combating Agent to form a chalcogenide film

本發明之另一態樣涉及使用控制試劑來對抗所述前驅物發生氣相預反應，而此預反應會導致基材上不均勻成核、沉積反應的培養時間拉長及生成膜的品質降低。此預反應尤其會對包含硫屬膜、相關來源材料(氧(O)、硫(S)、硒(Se)、碲(Te)、鍺(Ge)、銻(Sb)、鉍(Bi)等)之應用、及/或相變記憶體和熱電裝置的製造造成問題。Another aspect of the present invention relates to the use of a control agent to counteract the gas phase pre-reaction of the precursor, which causes a heterogeneous nucleation on the substrate, an elongated culture time for the deposition reaction, and a reduced quality of the resulting film. . This pre-reaction includes, inter alia, a chalcogenide film, a related source material (oxygen (O), sulfur (S), selenium (Se), tellurium (Te), germanium (Ge), antimony (Sb), antimony (Bi), etc. The application, and/or the fabrication of phase change memory and thermoelectric devices pose problems.

進行化學氣相沉積時，所述前驅物試劑引進沉積腔室後可能會發生預反應，其也可能發生於原子層沉積(ALD)製程，此視ALD循環步驟的安排和採用試劑而定。In chemical vapor deposition, a pre-reaction may occur after the precursor reagent is introduced into the deposition chamber, which may also occur in an atomic layer deposition (ALD) process, depending on the arrangement of the ALD cycle steps and the reagents employed.

故本發明包含使用控制試劑伴隨所述前驅物，以抑制、減緩或消除有害的氣相預反應，進而引起/增進基材表面之沉積反應，及有效形成特性優越的膜。Accordingly, the present invention encompasses the use of a control agent along with the precursor to inhibit, slow or eliminate harmful gas phase pre-reactions, thereby causing/promoting a deposition reaction on the surface of the substrate, and effectively forming a film having superior properties.

針對此目的而可配合本發明所述之前驅物使用的控制試劑包括選自由(i)異質原子(O、N、S)有機路易士(Lewis)鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑所組成群組之試劑。Controlling agents useful for this purpose in conjunction with the precursors of the present invention include those selected from the group consisting of (i) heteroatom atoms (O, N, S) organic Lewis base compounds, (ii) free radical inhibitors and Iii) Reagents containing a group consisting of hydrazine reagents.

這些試劑透過各種方式來減少所述前驅物產生有害的氣相預反應，包括：These agents are used in a variety of ways to reduce the harmful gas phase pre-reactions of the precursors, including:

(1)添加預反應抑制劑至前驅物組成內，包含一或多個異質原子(O、N、S)有機Lewis鹼化合物，例如1,4-二烷、氧硫(thioxane)、醚、聚醚、三乙胺(TEA)、三氮、二胺、N,N,N’,N’-四甲基乙二胺、N,N,N’-三甲基乙二胺、胺、亞胺和吡啶；(1) adding a pre-reaction inhibitor to the precursor composition, comprising one or more hetero-atomic atoms (O, N, S) organic Lewis base compounds, such as 1,4-two Alkane, oxysulfide (thioxane), ether, polyether, triethylamine (TEA), trinitrogen , diamine, N, N, N', N'-tetramethylethylenediamine, N, N, N'-trimethylethylenediamine, amine, imine and pyridine;

(2)添加自由基抑制劑至前驅物組成內，例如二丁基羥基甲苯(BHT)、氫醌、丁基羥基甲氧苯(BHA)、二苯胺、乙香草醛等；(2) adding a radical inhibitor to the precursor composition, such as dibutylhydroxytoluene (BHT), hydroquinone, butylhydroxymethoxybenzene (BHA), diphenylamine, ethamaldehyde, and the like;

(3)使用改質之硫屬前驅物，其中氫取代基已被氘(D)取代基所取代，而變成氘化類似物供氣相沉積之用；以及(3) using a modified chalcogen precursor in which the hydrogen substituent has been replaced by a ruthenium (D) substituent to become a deuterated analog for vapor deposition;

(4)添加氘源至前驅物組成內，藉以原位(in situ)氘化該前驅物。(4) Adding a ruthenium source to the precursor composition to thereby purify the precursor in situ.

上述抗預反應劑(抑制劑、自由基抑制劑、氘源及/或氘化前驅物)可引至氣相沉積製程中用於成膜的任何進料流。例如，抗預反應劑可引到一或多個前驅物進料流、隨後加入硫屬前驅物或其他試劑而流進沉積腔室的惰性載氣流、流入沉積腔室的共反應物進料流、及/或任何其他流入沉積腔室的氣流，且抗預反應劑可減少或消除前驅物在沒有抗預反應劑的情況下可能發生的預反應。The above anti-pre-reactants (inhibitors, free radical inhibitors, ruthenium sources and/or deuterated precursors) can be directed to any feed stream for film formation in a vapor deposition process. For example, an anti-reactant may be introduced into one or more precursor feed streams, followed by the addition of a chalcogenide precursor or other reagent to the inert carrier gas stream flowing into the deposition chamber, and the co-reactant feed stream flowing into the deposition chamber. And/or any other gas flow into the deposition chamber, and the anti-reactant reduces or eliminates the pre-reaction that the precursor may occur without the anti-reactant.

在特定實施例中，上述抑制劑、自由基抑制劑及/或氘源試劑是和前驅物(如金屬源試劑)一起注入，用以至少部分減少前驅物與試劑預先反應。In a particular embodiment, the inhibitor, free radical inhibitor, and/or ruthenium source reagent is injected with a precursor (eg, a metal source reagent) to at least partially reduce pre-reaction of the precursor with the reagent.

抗預反應劑或可直接加到沉積處，例如沉積腔室(在此，前驅物蒸氣引入並接觸基材而沉積膜於其上)，藉以抑制前驅物及/或其他試劑相關的有害氣相預反應。The anti-reactant may be added directly to the deposition site, such as a deposition chamber (here, the precursor vapor is introduced into and contacted with the substrate to deposit a film thereon), thereby inhibiting the harmful gas phase associated with the precursor and/or other reagents. Pre-reaction.

在另一方式中，廣泛應用本發明時，抑制劑、自由基抑制劑及/或氘源可加到含有前驅物及/或其他金屬源試劑的溶液內，所得溶液可用於液體輸送處理，其中溶液流入蒸發器以形成來源蒸氣而接觸基材及沉積沉積物種於其上。In another aspect, when the invention is widely used, the inhibitor, free radical inhibitor and/or hydrazine source can be added to a solution containing a precursor and/or other metal source reagent, and the resulting solution can be used for liquid transport processing, wherein The solution flows into the evaporator to form a source vapor to contact the substrate and deposit a deposition species thereon.

或者，若現存溶液不含前驅物及/或其他金屬源試劑，則可加入抑制劑、自由基抑制劑及/或氘源，以形成含前驅物及/或其他金屬源試劑的混合物或溶液，此視採用材料相和其相容性/溶解度而定。Alternatively, if the existing solution contains no precursors and/or other metal source reagents, inhibitors, free radical inhibitors, and/or helium sources may be added to form a mixture or solution containing the precursor and/or other metal source reagents. This depends on the material phase and its compatibility/solubility.

在又一方式中，基材接觸前驅物及/或其他金屬源試劑之前，抑制劑、自由基抑制劑及/或氘源可用來處理基材表面。In yet another aspect, the inhibitor, free radical inhibitor, and/or helium source can be used to treat the surface of the substrate prior to contacting the substrate with the precursor and/or other metal source reagents.

故本發明包含各種氣相沉積組成和成膜於基材上的製程，其中一或多個選自異質原子(O、N、S)有機Lewis鹼化合物的抗預反應劑(以下有時指抑制劑、自由基抑制劑及/或氘源試劑)係至少部分減弱前驅物的預先反應。除了利用氘源以原位氘化外，尚包含使用事先合成之氘化前驅物或有機金屬化合物。以這些方式抑制前驅物預先反應，可有效形成特性優越的膜。Therefore, the present invention comprises various vapor deposition compositions and processes for forming a film on a substrate, wherein one or more anti-pre-reactants selected from hetero-atomic (O, N, S) organic Lewis base compounds (hereinafter sometimes referred to as inhibition) The agent, free radical inhibitor and/or sputum source agent) at least partially attenuate the pre-reaction of the precursor. In addition to the use of helium source for in situ deuteration, it also involves the use of previously synthesized deuterated precursors or organometallic compounds. By suppressing the pre-reaction of the precursor in these manners, it is possible to form a film having excellent characteristics.

控制試劑可用來對抗硫屬前驅物在製程中的預先反應，其中多個進料流流到沉積處而成膜於基材上，其中多個進料流的至少一者包括易預先反應而不當影響膜的前驅物，且方法涉及將控制試劑引到多個進料流的至少一者或其供應材料、或引到沉積處。The control reagent can be used to counteract the pre-reaction of the chalcogen precursor in the process, wherein a plurality of feed streams flow to the deposition site to form a film on the substrate, wherein at least one of the plurality of feed streams comprises an easy pre-reaction A precursor that affects the membrane, and the method involves introducing a control reagent to at least one of the plurality of feed streams or a supply thereof, or to a deposit.

抗預反應劑或可引入以鈍化生長硫屬膜表面或減慢沉積速度，然後使用另一前驅物或共反應物(如氫氣(H2 )、氨氣(NH3 )、電漿、水(H2 O)、硫化氫、硒化氫、二取代基碲化物(diorganotelluride)、二取代基硫化物(diorganosulfide)、二取代基硒化物(diorganoselenide)等)再活化，從而例如按另一順序反覆施行鈍化/減慢(retardation)後再活化的步驟。在ALD製程或類ALD製程中，鈍化/減慢後再活化的過程可依需求反覆進行多次。這些步驟可在整個沉積操作過程、或於開始、中間或最後部分進行。The anti-reactant may be introduced to passivate the surface of the chalcogenide film or slow down the deposition rate, and then use another precursor or co-reactant (such as hydrogen (H 2 ), ammonia (NH 3 ), plasma, water ( H 2 O), hydrogen sulfide, hydrogen selenide, diorganotelluride, diorganosulfide, diorganoselenide, etc., are reactivated, for example, in another order The step of reactivation after passivation/retardation is performed. In an ALD process or an ALD-like process, the process of activation after deactivation/slowing can be repeated as many times as needed. These steps can be carried out throughout the deposition operation, or at the beginning, intermediate or final part.

故本發明包含包括前驅物與抗預反應劑的前驅物組成。在前述之抗預反應劑分類中，即(i)異質原子(O、N、S)有機Lewis鹼化合物、(ii)自由基抑制劑和(iii)含氘試劑，熟諳此技藝者可依據揭露內文輕易決定適合特殊應用的抗預反應劑。Thus, the invention comprises a precursor composition comprising a precursor and an anti-reactant. In the foregoing classification of anti-reactants, namely (i) heteroatomic (O, N, S) organic Lewis base compounds, (ii) free radical inhibitors, and (iii) ruthenium-containing reagents, those skilled in the art can disclose The text easily determines the anti-prereactor for a particular application.

異質原子(O、N、S)有機Lewis鹼化合物可為各種類型，例如含有側氧基(oxo；-O-)部分、氮環原子或懸垂胺基(pendant amino)或醯胺取代基、硫環原子或懸垂硫化物、磺酸鹽或硫基，用以至少部分減少前驅物和其他有機金屬試劑在處理系統中預先反應。用於本發明特殊應用的異質原子(O、N、S)有機Lewis鹼化合物例子包括1,4-二烷、氧硫、醚、聚醚、三乙胺、三氮、二胺、N,N,N’,N’-四甲基乙二胺、N,N,N’-三甲基乙二胺、胺、亞胺和吡啶等，但不以此為限。Heteroatomic (O, N, S) organic Lewis base compounds can be of various types, for example containing a pendant oxy (oxo; -O-) moiety, a nitrogen ring atom or a pendant amino or guanamine substituent, sulfur A ring atom or pendant sulfide, sulfonate or sulfur group is used to at least partially reduce the pre-reaction of the precursor and other organometallic reagents in the processing system. Examples of heteroatom (O, N, S) organic Lewis base compounds useful in the particular application of the invention include 1,4-two Alkane, oxysulfide , ether, polyether, triethylamine, trinitrogen , but not limited to, diamine, N, N, N', N'-tetramethylethylenediamine, N, N, N'-trimethylethylenediamine, amine, imine and pyridine.

在本發明之不同特定實施例中，異質原子有機Lewis鹼化合物包括胍基化合物，例如(Me2 N)2 C=NH。In various specific embodiments of the invention, the heteroatom atomic organic Lewis base compound comprises a mercapto compound such as (Me 2 N) 2 C=NH.

一較佳異質原子有機Lewis鹼化合物類型包括R3 N、R2 NH、RNH2 、R2 N(CH2 )x NR2 、R2 NH(CH2 )x NR2 、R2 N(CR2 )x NR2 與環胺(-N(CH2 )x -)、咪唑、噻吩、吡咯、噻唑、尿素、(oxazine)、哌喃、呋喃、吲哚、***、三氮、噻唑啉、唑、二硫(dithiane)、三硫、冠醚、1,4,7-三氮雜環壬烷、1,5,9-三氮雜環十二烷、1,4,7,10-四氮雜環十二烷(cyclen)、丁二醯胺、和上述之取代衍生物，其中R為氫基或任何適合的取代基部分(organo moiety)，例如氫基、C1 -C8 烷基、C1 -C8 烷氧基、C1 -C8 烯基、C1 -C8 炔基和C1 -C8 羧基，且x為1-6之整數。A preferred heteroatomic organic Lewis base compound type includes R 3 N, R 2 NH, RNH 2 , R 2 N(CH 2 ) x NR 2 , R 2 NH(CH 2 ) x NR 2 , R 2 N (CR 2 x NR 2 with cyclic amines (-N(CH 2 ) x -), imidazole, thiophene, pyrrole, thiazole, urea, (oxazine), piperazine, furan, hydrazine, triazole, trinitrogen Thiazoline, Oxazole, disulfide (dithiane), trisulfide , crown ether, 1,4,7-triazacyclononane, 1,5,9-triazacyclododecane, 1,4,7,10-tetraazacyclododecane, Butane amine, and a substituted derivative thereof, wherein R is a hydrogen group or any suitable organo moiety such as a hydrogen group, a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, C 1 -C 8 alkenyl, C 1 -C 8 alkynyl and C 1 -C 8 carboxyl, and x is an integer from 1 to 6.

前驅物組成中的異質原子有機Lewis鹼化合物可具任何適當濃度，例如可相繼改變異質原子有機Lewis鹼化合物濃度來進行沉積及評估生成膜特性，以決定適當濃度。在不同實施例中，異質原子有機Lewis鹼化合物的使用濃度可為前驅物總量的1-300%。不需過度實驗即可依據揭露內文決定特殊前驅物類型介於異質原子有機Lewis鹼化合物之0.01-3當量內的特殊濃度子範圍。The heteroatom atomic organic Lewis base compound in the precursor composition can be deposited at any suitable concentration, for example, by sequentially varying the concentration of the heteroatom atomic organic Lewis base compound and evaluating the resulting film properties to determine the appropriate concentration. In various embodiments, the heteroatom atomic organic Lewis base compound can be used at a concentration of from 1 to 300% of the total amount of the precursor. The special concentration sub-range of the specific precursor type within 0.01-3 equivalents of the hetero-atomic organic Lewis base compound can be determined according to the disclosure without undue experimentation.

抗預反應劑或可或另可包含自由基抑制劑，用以有效減少前驅物與其他有機金屬試劑間的預反應。自由基抑制劑可為任何適合類型，例如包括受阻酚系(hindered phenols)。示例之自由基抑制劑包括選自由2,6-二第三丁基-4-甲基酚、2,2,6,6-四甲基-哌啶-1-氧、2,6-二甲基酚、2-第三丁基-4-羥基甲氧苯、3-第三丁基-4-羥基甲氧苯、3,4,5-三羥基苯甲酸丙酯、2-(1,1-甲基乙基)-1,4-苯二酚、二苯苦醯肼(diphenylpicrylhydrazyl)、4-第三丁基鄰苯二酚、N-甲苯胺、2,6-二甲基苯胺、對甲氧基二苯胺、二苯胺、N,N’-二苯基對苯二胺、對羥基二苯胺、酚、3-(3,5-二第三丁基-4-羥基苯)丙酸十八酯、肆[亞甲基(3,5-二第三丁基-4-羥基)苯丙酸]季戊四醇酯(tetrakis(methylene(3,5-di-tert-butyl-4-hydroxy-hydrocinnamate)methane)、啡噻(phenothiazine)、烷脒基異脲(alkylamidoisourea)、二(3,5-二第三丁基-4-羥基)苯丙酸硫代二乙烯酯(thiodiethylene bis(3,5,-di-tert-butyl-4-hydroxy-hydrocinnamate)、1,2-二(3,5-二第三丁基-4-羥基桂皮醯)肼(1,2,-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine)、三(2-甲基-4-羥基-5-第三丁基苯)丁烷、環新戊烷二亞磷酸十八酯(cyclic neopentanetetrayl bis(octadecyl phosphite))、4,4’-硫代雙(6-第三丁基間甲酚)、2,2’-亞甲基雙(6-第三丁基對甲酚)、草酸雙苯基亞甲基醯肼(oxalyl bis(benzylidenehydrazide))、和其混合物組成群組之自由基捕捉劑(scavenger)，但不以此為限。較佳的自由基抑制劑包括BHT、BHA、二苯胺、乙香草醛等。The anti-reactant may or may additionally comprise a free radical inhibitor to effectively reduce the pre-reaction between the precursor and other organometallic reagents. The free radical inhibitor can be of any suitable type, including, for example, hindered phenols. Exemplary free radical inhibitors include those selected from the group consisting of 2,6-di-t-butyl-4-methylphenol, 2,2,6,6-tetramethyl-piperidine-1-oxo, 2,6-dimethyl Phenolic acid, 2-tert-butyl-4-hydroxymethoxybenzene, 3-tert-butyl-4-hydroxymethoxybenzene, propyl 3,4,5-trihydroxybenzoate, 2-(1,1 -methylethyl)-1,4-benzenediol, diphenylpicrylhydrazyl, 4-tert-butyl catechol, N-toluidine, 2,6-dimethylaniline, pair Methoxydiphenylamine, diphenylamine, N,N'-diphenyl-p-phenylenediamine, p-hydroxydiphenylamine, phenol, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid Octaester, hydrazine [methylene (3,5-di-t-butyl-4-hydroxy) phenylpropanoic acid] pentaerythritol (tetrakis (methylene (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate) Methane) (phenothiazine), alkylamidoisourea, thiodiethylene bis (3,5,-di-tert- Butyl-4-hydroxy-hydrocinnamate), 1,2-bis(3,5-di-t-butyl-4-hydroxy cinnabarin)肼 (1,2,-bis(3,5-di-tert-butyl-) 4-hydroxyhydrocinnamoyl)hydrazine), tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, cyclopentanetetrayl bis(octadecyl phosphite), 4 , 4'-thiobis(6-t-butyl-m-cresol), 2,2'-methylenebis(6-t-butyl-p-cresol), bisphenylmethylene oxalate Oxalyl bis(benzylidenehydrazide), and mixtures thereof, constitute a group of free radical scavengers, but not limited thereto. Preferred free radical inhibitors include BHT, BHA, diphenylamine, ethamaldehyde and the like.

在不同特定實施例中，自由基抑制劑的有效濃度範圍按前驅物重量計為約0.001-0.10重量%。更廣泛地說，任何適量的自由基抑制劑皆可用來有效對抗前驅物於成膜製程的輸送及沉積操作期間預先反應。In various specific embodiments, the effective concentration of the free radical inhibitor ranges from about 0.001 to 0.10% by weight based on the weight of the precursor. More broadly, any suitable amount of free radical inhibitor can be used to effectively counteract the pre-reaction of the precursor during the transport and deposition operations of the film forming process.

氘源化合物為抑制硫屬前驅物預先反應的另一方式。氘源化合物可為任何適合類型，例如包括氘化吡啶、氘化嘧啶、氘化吲哚、氘化咪唑、氘化胺與醯胺化合物、氘化烷化劑等、和含有氫基或質子取代基之前驅物的氘化類似物。The ruthenium compound is another way to inhibit the pre-reaction of the chalcogen precursor. The ruthenium-derived compound may be of any suitable type, including, for example, deuterated pyridine, pyridinium pyrimidine, antimony telluride, deuterated imidazole, deuterated amine and decylamine compound, deuterated alkylating agent, etc., and containing hydrogen or proton substitution. A deuterated analog of the precursor.

做為本發明抗預反應劑應用的氘化物包括化學式為Rx GeD4-x 和Rx SbD3-x 的鍺與銻化合物，其中R為氫基或任何適合的取代基部分，例如氫基、C1 -C8 烷基、C1 -C8 烷氧基、C1 -C8 烯基、C1 -C8 炔基和C1 -C8 羧基，且x為1-6之整數，但不以此為限。As the present invention against a pre-application of the reactant deuterated comprises R x GeD 4-x and germanium, and antimony compounds R x SbD 3-x has the formula wherein R is a hydrogen group or any suitable substituent moieties, e.g. hydrogen group a C 1 -C 8 alkyl group, a C 1 -C 8 alkoxy group, a C 1 -C 8 alkenyl group, a C 1 -C 8 alkynyl group and a C 1 -C 8 carboxyl group, and x is an integer of from 1 to 6, But not limited to this.

氘源試劑可具任何適當濃度來有效對抗前驅物的預反應。在本發明之特定實施例中，氘源試劑的濃度按前驅物重量計例如為約0.01-5重量%。The ruthenium reagent can be at any suitable concentration to effectively counteract the pre-reaction of the precursor. In a particular embodiment of the invention, the concentration of the ruthenium source reagent is, for example, from about 0.01% to about 5% by weight based on the weight of the precursor.

因此，氘源化合物可加至氣相沉積製程的一或多個進料流，及/或前驅物或其他進料流化合物可先行氘化。Thus, the ruthenium compound can be added to one or more feed streams of the vapor deposition process, and/or the precursor or other feed stream compound can be deuterated first.

本發明用來至少部分消除前驅物預先反應的抗預反應劑濃度在施行本發明時可大幅改變，此視溫度、壓力、流速和採用組成物而定。應理解上述抗預反應劑的濃度範圍僅為舉例說明，熟諳此技藝者可依據揭露內文輕易決定應用濃度。The concentration of the anti-reactant used in the present invention to at least partially eliminate the pre-reaction of the precursor can vary widely depending on the temperature, pressure, flow rate and composition employed in the practice of the present invention. It should be understood that the concentration ranges of the above anti-pre-reactants are merely illustrative, and those skilled in the art can easily determine the application concentration according to the disclosure.

引進或加入抗預反應劑至沉積製程之一或多個進料流的特定模式可相應地改變，例如使用質流控制器、流量控制閥、計量注射器、或其他流量控制或調節組件，其設於流路(flow circuitry)，以於一般成膜操作時連接抗預反應劑源和待流入沉積製程之氣流。處理系統另可依需求或本發明特定實施例而包括分析儀、監視器、控制器、測試儀器等。The particular mode of introducing or adding the anti-reactant to one or more of the feed processes may be varied accordingly, such as using a mass flow controller, flow control valve, metering injector, or other flow control or conditioning assembly. In flow circuitry, the source of the anti-reactant and the gas stream to be flowed into the deposition process are connected during a typical film forming operation. The processing system may additionally include analyzers, monitors, controllers, test instruments, etc., as desired or in particular embodiments of the invention.

除了引進或加入抗預反應劑至氣相沉積製程之一或多個進料流外，抗預反應劑可先與前驅物混合當作製程的起始劑材料。例如，抗預反應劑和前驅物可混於液體溶液，再將形成之前驅物溶液輸送到蒸發器，以產生前驅物蒸氣而接觸基材及沉積膜於其上。In addition to introducing or adding an anti-pre-reactant to one or more of the vapor-depositing processes, the anti-reactant may be first mixed with the precursor as the starting material for the process. For example, the anti-pre-reactant and the precursor may be mixed with the liquid solution, and the precursor-forming solution is transported to the evaporator to produce precursor vapor to contact the substrate and deposit the film thereon.

如前所述，添加抗預反應劑於沉積處可主動抑制前驅物蒸氣發生氣相預反應，以免造成不當影響。As mentioned above, the addition of the anti-pre-reactant at the deposition site can actively suppress the gas phase pre-reaction of the precursor vapor to avoid undue influence.

又或者，抗預反應劑可用於初步表面處理，接著前驅物和共反應物(如H2 、NH3 、電漿、H2 O、硫化氫、硒化氫、二取代基碲化物、二取代基硫化物、二取代基硒化物等)再輸送到基材表面及沉積至表面。為此，在開始流入任何前驅物前，可先將抗預反應劑引到沉積製程的一或多個流動管線並流向沉積處理腔室的基材。使基材接觸抗預反應劑一段必要時間後，停止流入抗預反應劑，並開始讓一般氣流流進沉積腔室。Alternatively, the anti-reactant can be used for preliminary surface treatment followed by precursors and co-reactants (eg, H 2 , NH 3 , plasma, H 2 O, hydrogen sulfide, hydrogen selenide, disubstituted telluride, disubstituted) The base sulfide, disubstituted selenide, etc.) are transported to the surface of the substrate and deposited onto the surface. To this end, the anti-pre-reactant may be directed to one or more flow lines of the deposition process and to the substrate of the deposition processing chamber prior to beginning to flow into any of the precursors. After the substrate is brought into contact with the anti-reactant for a necessary period of time, the flow of the anti-pre-reactant is stopped and a general gas flow is started to flow into the deposition chamber.

從以上敘述得知，抗預反應劑可以各種方式引用來有效減少前驅物在沉積系統中預先反應。From the above description, the anti-reactant can be cited in various ways to effectively reduce the pre-reaction of the precursor in the deposition system.

在本發明之一實施例中，包含氣相沉積系統，其包含：一氣相沉積腔室，適於支托住至少一基材，以於該基材上沉積一膜；化學試劑供應容器，含有成膜試劑；第一流路，用以將試劑從化學試劑供應容器輸送到氣相沉積腔室；一抗預反應劑供應容器，含有抗預反應劑；第二流路，用以將抗預反應劑從抗預反應劑供應容器輸送到第一流路、化學試劑供應容器及/或氣相沉積腔室。In one embodiment of the present invention, a vapor deposition system comprising: a vapor deposition chamber adapted to support at least one substrate to deposit a film on the substrate; a chemical reagent supply container containing a film forming reagent; a first flow path for transporting the reagent from the chemical reagent supply container to the vapor deposition chamber; an anti-prereactant supply container containing the anti-pre-reactant; and a second flow path for resisting the pre-reaction The agent is delivered from the anti-reactant supply container to the first flow path, the chemical reagent supply container, and/or the vapor deposition chamber.

現參照圖式，第4圖為根據一實施例之氣相沉積系統100的示意圖。Referring now to the drawings, FIG. 4 is a schematic illustration of a vapor deposition system 100 in accordance with an embodiment.

在此示例系統中，抗預反應劑容設於供應容器110中。抗預反應劑包含預反應抑制劑、自由基抑制劑、氘源、或其二或多個此種試劑及/或此種試劑類型的組合物。In this example system, the anti-prereactor is contained in the supply container 110. The anti-reactant comprises a pre-reaction inhibitor, a free radical inhibitor, a hydrazine source, or a combination thereof of two or more such agents and/or such reagent types.

抗預反應劑供應容器分別透過流動管線112、114、116連接鍺、銻、碲試劑供應容器(分別標示”G”、”S”和”T”)。容器”G”內的鍺前驅物可為四烷基或四醯胺基鍺化合物，例如四甲鍺、四乙鍺、四烯丙鍺、肆(二甲胺基)鍺烷或其他有機鍺化合物。另外，前驅物”G”可為鍺烯(germylene)化合物，其中Ge(II)上的孤對電子在沒有預反應抑制劑的情況下會與硫屬前驅物產生氣相反應。容器”S”內的銻前驅物可為三烷基或三醯胺基銻化合物，例如三丁銻、三異丙銻、三(二甲胺基)銻或其他有機銻化合物。容器”T”內的碲前驅物可為二烷基或二醯胺基碲化合物，例如二異丙碲、二丁碲、雙[雙(三甲矽烷基)胺基]碲或其他有機碲化合物。The anti-reactant supply container is connected to the 锗, 锑, 碲 reagent supply containers (labeled "G", "S" and "T", respectively) through the flow lines 112, 114, 116, respectively. The ruthenium precursor in the vessel "G" may be a tetraalkyl or tetraammonium ruthenium compound such as tetramethyl hydrazine, tetraethylene hydrazine, tetraallyl hydrazine, hydrazine (dimethylamino) decane or other organic hydrazine compound. . Alternatively, the precursor "G" may be a germem compound in which a lone pair of electrons on Ge(II) reacts with a chalcogen precursor in the absence of a pre-reaction inhibitor. The ruthenium precursor in the vessel "S" may be a trialkyl or triammonium ruthenium compound such as tributyl sulfonium, triisopropyl hydrazine, tris(dimethylamino) hydrazine or other organic hydrazine compound. The ruthenium precursor in the vessel "T" may be a dialkyl or diammonium ruthenium compound such as diisopropyl hydrazine, dibutyl hydrazine, bis[bis(trimethyl decyl)amino] hydrazine or other organic hydrazine compound.

故抗預反應劑可經由各對應流動管線添加至容器”G”、”S”或”T”內的任何鍺、銻及/或碲前驅物，管線為此設有流量控制閥或其他流量調節組件。Therefore, the anti-reactant can be added to any helium, neon and/or ruthenium precursor in the vessel "G", "S" or "T" via each corresponding flow line, and the pipeline is provided with a flow control valve or other flow regulation for this purpose. Component.

在所示之特定製程實施例中，液態鍺、銻和碲前驅物分別從進料管線118、120、122流入混合腔室124，形成之前驅物混合物接著從混合腔室124而由管線126內流到蒸發器128。在蒸發器中，液態前驅物混合物和抗預反應劑揮發成前驅物蒸氣。前驅物蒸氣接著從管線130內流向氣相沉積腔室132的噴灑頭分散器134，以將前驅物混合物排放到置於沉積腔室之基座138上的晶圓基材136。In the particular process embodiment shown, liquid helium, neon, and krypton precursors flow from feed lines 118, 120, 122 into mixing chamber 124, respectively, forming a precursor mixture followed by mixing chamber 124 from line 126. Flow to evaporator 128. In the evaporator, the liquid precursor mixture and the anti-prereactor are volatilized into a precursor vapor. The precursor vapor then flows from line 130 to a showerhead disperser 134 of vapor deposition chamber 132 to discharge the precursor mixture to wafer substrate 136 disposed on pedestal 138 of the deposition chamber.

接觸晶圓基材136的前驅物蒸氣係用來沉積鍺、銻和碲金屬於基材上，而形成鍺銻碲(GST)材料薄膜，其例如用於製造相變隨機存取記憶體裝置。The precursor vapor contacting the wafer substrate 136 is used to deposit tantalum, niobium and tantalum metal onto the substrate to form a thin film of germanium (GST) material, for example, for fabricating a phase change random access memory device.

耗盡金屬含量的接觸前驅物蒸氣從氣相沉積腔室132而由管線140內流到流出物減弱單元142。在流出物減弱單元142中，例如藉由刷洗、催化氧化、電化學處理或其他方式來處理排放的流出蒸氣，以產生最終流出物，該最終流出物從減弱單元而由管線146內排出。The metal precursor-depleted contact precursor vapor flows from the vapor deposition chamber 132 from the inside of the line 140 to the effluent abatement unit 142. In the effluent abatement unit 142, the effluent effluent vapor is treated, for example, by scrubbing, catalytic oxidation, electrochemical treatment, or other means to produce a final effluent that is withdrawn from the abatement unit and from line 146.

將可理解第4圖所示之氣相沉積系統僅為舉例說明而已，此當可配置成其他排列方式及使用抗預反應劑，包括前述方式。例如，抗預反應劑可直接引進混合腔室124，使之與各GST前驅物在混合腔室124內混合。或者，抗預反應劑可引至歧管118或其他混合腔室、攪拌器等，以結合待輸送到沉積處的前驅物。It will be understood that the vapor deposition system illustrated in Figure 4 is for illustrative purposes only, and may be configured in other arrangements and using anti-pre-reactants, including the foregoing. For example, the anti-reactant can be introduced directly into the mixing chamber 124 to be mixed with the respective GST precursors in the mixing chamber 124. Alternatively, the anti-reactant can be directed to manifold 118 or other mixing chamber, agitator, etc. to incorporate the precursor to be delivered to the deposit.

第4圖系統採用液體輸送各前驅物的方式。將可理解，若使用固態前驅物，則可利用固體輸送技術，其中固態前驅物例如因固態起始材料昇華而揮發。The system of Figure 4 uses a liquid to transport each precursor. It will be appreciated that if a solid precursor is used, solid delivery techniques can be utilized in which the solid precursor is volatilized, for example, by sublimation of the solid starting material.

除了使用氘化試劑做為第4圖系統的抗預反應劑外，也可先供應一或多個鍺、銻和碲前驅物當作有機鍺、銻或碲前驅物的氘化類似物，其中有機部分的氫取代基已被氘取代。In addition to the use of deuteration reagents as anti-prereactors for the system of Figure 4, one or more of the ruthenium, osmium and iridium precursors may be supplied as deuterated analogs of organic ruthenium, osmium or iridium precursors, among which The hydrogen substituent of the organic moiety has been replaced by deuterium.

本發明抗預反應劑可廣泛應用來形成用於半導體產品製造的改良膜。所述抗預反應劑一般可用於各種特殊應用組合，以抑制或消除前驅物預先反應及提供良好的成核作用和最終膜性質。The anti-prereactor of the present invention can be widely applied to form improved films for the manufacture of semiconductor products. The anti-reactant can generally be used in a variety of specific application combinations to inhibit or eliminate precursor pre-reaction and to provide good nucleation and final film properties.

液體輸送配方Liquid delivery formula

採用之液體輸送配方的前驅物可為純液態形式，或者液態或固態前驅物可備於適當溶劑，例如包括烷烴溶劑(如己烷、庚烷、辛烷和戊烷)、芳香羥溶劑(如苯或甲苯)、胺(如三乙胺、三級丁胺)、亞胺和肼、或其混合物。用於特殊Te前驅物的溶劑組成物可憑經驗輕易決定，以選出適合的單一成分或多重成分溶劑介質供液體輸送蒸發及輸送採用的特定銻前驅物。若本發明採用固態前驅物，則可利用固體輸送系統，例如ProE-VapTM 固體輸送與蒸發單元(其可購自美國康乃迪克州丹博瑞市的ATMI公司)。The precursor of the liquid delivery formulation may be in pure liquid form, or the liquid or solid precursor may be prepared in a suitable solvent, for example, including an alkane solvent (such as hexane, heptane, octane, and pentane), an aromatic hydroxy solvent (such as Benzene or toluene), an amine such as triethylamine, tertiary butylamine, imine and hydrazine, or a mixture thereof. The solvent composition for the particular Te precursor can be readily determined empirically to select a suitable single component or multiple component solvent medium for liquid transport to evaporate and transport the particular ruthenium precursor used. If the present invention employs a solid precursor, a solids delivery system such as a ProE-Vap (TM) solids delivery and evaporation unit (available from ATMI, Inc., of Danbury, Connecticut) can be utilized.

一般來說，利用本發明前驅物所形成之含金屬層的厚度可為任何適當值。在本發明一特定實施例中，含銻層的厚度為5奈米(nm)至500nm或以上(包括平面和溝渠/通孔幾何形狀)。In general, the thickness of the metal-containing layer formed using the precursor of the present invention can be any suitable value. In a particular embodiment of the invention, the germanium containing layer has a thickness from 5 nanometers (nm) to 500 nm or more (including planar and trench/via geometry).

本發明之不同銻前驅物化合物可結合任何適合的鍺與銻前驅物，並例如利用CVD和ALD技術來形成GST膜，以用於如PCRAM裝置之應用。熟諳此技藝者可選擇性改變輸送與沉積製程條件及記述生成膜特性，以權衡判斷最適合特定沉積應用的製程條件封套，而輕易決定進行含Sb膜沉積的製程條件。The different ruthenium precursor compounds of the present invention can be combined with any suitable ruthenium and osmium precursors and formed into GST films, for example, using CVD and ALD techniques, for applications such as PCRAM devices. Those skilled in the art can selectively vary the transport and deposition process conditions and characterize the resulting film to balance the process conditions that best suit the particular deposition application, and easily determine the process conditions for the Sb-containing film deposition.

在一些實施例中，含銻膜例如利用原子層沉積(ALD)或化學氣相沉積(CVD)技術形成在基材上，其例如為GST膜、無定形SbTe膜或結晶SbTe膜。SbTe膜(如Sb2 Te3 )也可應用於熱電裝置。In some embodiments, the ruthenium containing film is formed on the substrate, for example, by atomic layer deposition (ALD) or chemical vapor deposition (CVD) techniques, such as a GST film, an amorphous SbTe film, or a crystalline SbTe film. SbTe films such as Sb 2 Te 3 can also be applied to thermoelectric devices.

在另一實施例中，無定形(amorphous)SbTe可在溫度為250℃-400℃(如320℃)下、流速每分鐘為20-50標準毫升(sccm)(如30sccm)的惰性載氣流(如N2 )中，利用起泡器輸送含銻和碲前驅物，以共沉積所述含銻化合物和碲前驅物(如二第三丁基碲(Te(t Bu)2 )或二異丙基碲(Te(i Pr)2 ))而製得。用於沉積之碲和銻前驅物可為任何適合類型，並可按任何適當體積流速輸送前驅物進行沉積，例如上述示例碲前驅物(Te(t Bu)2 )的流速為30sccm，含銻前驅物的流速為5微莫耳/分鐘。形成之無定形SbTe膜的銻含量為約20%-70%。In another embodiment, the amorphous SbTe can be an inert carrier gas stream at a flow rate of from 250 ° C to 400 ° C (eg, 320 ° C) at a flow rate of from 20 to 50 standard milliliters (sccm) per minute (eg, 30 sccm) ( For example, in N 2 ), a ruthenium- and ruthenium-containing precursor is transported by a bubbler to co-deposit the ruthenium-containing compound and a ruthenium precursor (such as di-tert-butyl fluorene (Te( t Bu) 2 ) or diisopropyl). It is made based on Te( i Pr) 2 ). The ruthenium and osmium precursors used for deposition may be of any suitable type and may be deposited by transporting the precursor at any suitable volumetric flow rate, such as the above-described example ruthenium precursor (Te( t Bu) 2 ) having a flow rate of 30 sccm, containing ruthenium precursors. The flow rate of the material was 5 micromoles per minute. The amorphous SbTe film formed has a cerium content of about 20% to 70%.

第1圖為根據本發明一實施例之材料儲存與分配封裝件200的示意圖，其含有銻前驅物。1 is a schematic illustration of a material storage and dispensing package 200 containing a ruthenium precursor, in accordance with an embodiment of the present invention.

材料儲存與分配封裝件100包括如大致呈圓柱狀的容器102，其內界定出一內部容積104。在此特定實施例中，前驅物在周圍(ambient)溫度條件下為固體，且前驅物可支托在容器內部容積104的托盤106表面上，托盤設有相連之流通導管108，供容器內的蒸氣向上流至閥頭組件，以使用容器進行分配。The material storage and dispensing package 100 includes a generally cylindrical container 102 defining an interior volume 104 therein. In this particular embodiment, the precursor is solid under ambient temperature conditions and the precursor can be supported on the surface of the tray 106 of the interior volume 104 of the container, the tray being provided with an associated flow conduit 108 for the interior of the container The vapor flows up to the valve head assembly for dispensing using the container.

固態前驅物可覆蓋在容器內部容積的內面上，例如托盤106和導管108的表面上。引進氣相前驅物至容器後，其將凝結成固態前驅物膜於容器表面而造成上述覆蓋。或者，固態前驅物可溶解或懸浮於溶劑介質中，並藉由溶劑揮發而沉積在容器內部容積的表面。又一方法則是熔化前驅物及將其倒到容器內部容積的表面上。為此，容器包含板件或元件，以提供額外的容器表面區域來支撐前驅物膜於其上。The solid precursor can cover the inner surface of the interior volume of the container, such as the surface of the tray 106 and conduit 108. Upon introduction of the vapor precursor to the vessel, it will condense into a solid precursor film on the surface of the vessel causing the above coverage. Alternatively, the solid precursor can be dissolved or suspended in a solvent medium and deposited on the surface of the interior volume of the container by evaporation of the solvent. Yet another method is to melt the precursor and pour it onto the surface of the interior volume of the container. To this end, the container contains panels or elements to provide additional container surface areas to support the precursor film thereon.

又或者，固態前驅物為粒狀或細粉，其倒入容器中且留在托盤106的上支撐面上。又或者，容器內部容積設有金屬發泡主體，其具備特殊特性的多孔性而留住前驅物固體，藉以有效揮發前驅物。Still alternatively, the solid precursor is a granular or fine powder that is poured into a container and left on the upper support surface of the tray 106. Alternatively, the inner volume of the container is provided with a metal foaming body having a special characteristic of porosity to retain the precursor solids, thereby effectively volatilizing the precursor.

容器102設有連結閥頭組件110的頸部109。在此實施例中，閥頭組件裝配手動輪112。除了手動輪外，閥頭組件也可耦接或操作連接至控制器而自動操作。閥頭組件110包括分配埠114，其係配置以耦接接頭配件或連接元件以連結流路和容器。流路以第1圖箭頭A表示，且流路可耦接至下游ALD或化學氣相沉積腔室(第1圖未繪示)。The container 102 is provided with a neck 109 that joins the valve head assembly 110. In this embodiment, the valve head assembly is fitted with a manual wheel 112. In addition to the manual wheel, the valve head assembly can also be coupled or operatively coupled to the controller for automatic operation. The valve head assembly 110 includes a dispensing jaw 114 that is configured to couple a fitting or connecting element to join the flow path and the container. The flow path is indicated by arrow A of Figure 1, and the flow path can be coupled to a downstream ALD or chemical vapor deposition chamber (not shown in Figure 1).

使用時，利用適合之加熱器(如固定在容器外部壁面的加熱套、電阻式加熱元件等)來加熱容器102，使容器內的固態前驅物至少部分揮發成前驅物蒸氣。輸入熱以第1圖參考箭頭Q表示。當手動輪112或其他閥致動器或控制器轉成開閥位置時，前驅物蒸氣將分配到箭頭A所示的流路中，導致前驅物蒸氣經由閥頭組件110的閥通道排出容器。In use, the container 102 is heated using a suitable heater (such as a heating jacket attached to the outer wall of the container, a resistive heating element, etc.) to at least partially volatilize the solid precursor within the container into precursor vapor. The input heat is indicated by the reference arrow Q in Fig. 1. When the manual wheel 112 or other valve actuator or controller is turned into the open position, the precursor vapor will be distributed into the flow path shown by arrow A, causing the precursor vapor to exit the container via the valve passage of the valve head assembly 110.

除了固體輸送前驅物外，前驅物也可備於溶劑介質而形成溶液或懸浮液。此含前驅物之溶劑組成接著以液體輸送方式輸送，並經急驟汽化產生前驅物蒸氣。前驅物蒸氣在沉積條件下接觸基材，因而沉積金屬膜於基材上。In addition to the solid transport precursor, the precursor can also be prepared in a solvent medium to form a solution or suspension. The solvent composition of the precursor is then transported by liquid transport and is rapidly vaporized to produce a precursor vapor. The precursor vapor contacts the substrate under deposition conditions, thereby depositing a metal film on the substrate.

在一實施例中，前驅物溶於離子液體介質，前驅物蒸氣在分配條件下抽離離子液體溶液。In one embodiment, the precursor is dissolved in an ionic liquid medium and the precursor vapor is evacuated from the ionic liquid solution under dispensing conditions.

又或者，前驅物的儲存方式為吸附在容器內部容積中適合的固相物理吸附儲存介質。使用時，在包括吸附之前驅物自固相物理吸附儲存介質脫附的分配條件下，分配來自容器的前驅物蒸氣。Alternatively, the precursor is stored in a manner suitable for solid phase physical adsorption storage media in the interior volume of the container. In use, the precursor vapor from the vessel is dispensed under dispensing conditions that include desorption of the precursor from the solid phase physical adsorption storage medium prior to adsorption.

用於輸送前驅物的供應容器可為各種類型，且可採用市售容器來儲存及分配本發明之特殊前驅物，例如取自ATMI公司(位於美國康乃迪克州丹博瑞市)的商品SDS、SAGE、VAC、VACSorb和ProE-Vap。The supply containers for transporting the precursors can be of various types, and commercially available containers can be used to store and dispense the particular precursors of the present invention, such as the product SDS available from ATMI (Danbury, Connecticut). , SAGE, VAC, VACSorb, and ProE-Vap.

本發明之前驅物可用來形成前驅物蒸氣，進而接觸基材以沉積含銻薄膜於其上。The precursor of the present invention can be used to form a precursor vapor which in turn contacts the substrate to deposit a ruthenium containing film thereon.

在一較佳態樣中，本發明採用前驅物進行原子層沉積來形成共形性佳的ALD膜，即便是覆蓋高深寬比結構，其仍均勻覆蓋在基材上且具良好的階梯覆蓋性和共形性。In a preferred embodiment, the present invention employs a precursor for atomic layer deposition to form a conformal ALD film which evenly covers the substrate and has good step coverage even if it covers a high aspect ratio structure. And conformality.

因此，本發明之前驅物可廣泛應用到各種具優良品質之含銻膜的微電子裝置，例如半導體產品、平面顯示器等。Therefore, the precursor of the present invention can be widely applied to various microelectronic devices containing excellent quality, such as semiconductor products, flat panel displays, and the like.

本發明在參閱以下非限定實施例後將變得更清楚易懂。The invention will become more apparent and understood from the following non-limiting examples.

實施例1：製備(Example 1: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)SbCl一般程序Bu) SbCl general procedure

除非特別指明，否則皆於乾燥氮氣大氣中利用乾燥箱或標準Schlenk技術進行所有操作。苯-d6 以4埃分子篩乾燥。Mercury 300MHz傅立葉轉換(FT)光譜儀在21℃下記錄NMR圖譜，並以溶劑(1 H光譜中的殘餘質子)做為參考基準。備於己烷之正丁基鋰(n-BuLi)(1.6M)和N,N’-二異丙基碳二亞胺購自Aldirch且按接收到的原樣使用。氯化鍺(GeCl2 )-二烷購自Gelest。四氫呋喃(THF)、醚和戊烷購自Aldirch，並在使用之前利用溶劑乾燥系統和活性氧化鋁/分子篩管柱加以乾燥。All operations were carried out in a dry nitrogen atmosphere using a dry box or standard Schlenk technique unless otherwise specified. Benzene-d 6 was dried over 4 angstrom molecular sieves. The Mercury 300 MHz Fourier Transform (FT) spectrometer recorded the NMR spectra at 21 ° C with reference to the solvent (residual protons in the 1 H spectrum). n-Butyllithium (n-BuLi) (1.6 M) and N,N'-diisopropylcarbodiimide prepared in hexane were purchased from Aldirch and used as received. Barium chloride (GeCl 2 )-two The alkane was purchased from Gelest. Tetrahydrofuran (THF), ether and pentane were purchased from Aldirch and dried using a solvent drying system and an activated alumina/molecular sieve column prior to use.

在冰浴中對備於二***(650毫升)的N,N’-二第三丁基乙二胺(37.8克、47.2毫升、219毫莫耳)、三乙胺(44.4克、60.8毫升、438毫莫耳)溶液進行冷卻。慢慢加入備於醚(100毫升)中的三氯化銻(50.0克、219毫莫耳)，以形成濃稠白色沉澱物。將混合物保持呈室溫且攪拌整個晚上。接著在氮氣中過濾混合物(中級玻料)，及在真空下使亮黃色溶液揮發成淺黃色固體。利用真空昇華(50℃油浴、50毫托耳、<-5℃冷指)純化化合物整個晚上。如此可得55.5克、77%之半結晶白色粉末。1 H NMR(C6 D6 )：3.38、3.12(m,4H,CH2 CH2 )、1.18(s,18H,t -Bu)。13 C NMR(C6 D6 )：55.77(CR4 )、51.54(CH2 CH2 )、31.48(CH3 )。C10 H22 N2 SbCl的分析計算值：C(36.67)；H(6.77)；N(8.55)。實驗值：C(36.71)；H(7.06)；N(8.58)。N,N'-di-t-butylethylenediamine (37.8 g, 47.2 ml, 219 mmol) and triethylamine (44.4 g, 60.8 ml, prepared in diethyl ether (650 ml) in an ice bath. The solution was cooled at 438 mmol. Cesium trichloride (50.0 g, 219 mmol) in ether (100 mL) was slowly added to form a thick white precipitate. The mixture was kept at room temperature and stirred overnight. The mixture was then filtered under nitrogen (intermediate glass) and the bright yellow solution was evaporated to a pale yellow solid under vacuum. The compound was purified overnight by vacuum sublimation (50 ° C oil bath, 50 mTorr, <-5 ° C cold finger). Thus, 55.5 g, 77% of a semi-crystalline white powder was obtained. 1 H NMR (C 6 D 6 ): 3.38, 3.12 (m, 4H, CH 2 CH 2 ), 1.18 (s, 18H, t -Bu). 13 C NMR (C 6 D 6 ): 55.77 (CR 4 ), 51.54 (CH 2 CH 2 ), 31.48 (CH 3 ). For C 10 H 22 N 2 SbCl: C (36.67); H (6.77); N (8.55). Found: C (36.71); H (7.06); N (8.58).

實施例2：製備(Example 2: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)SbNMeBu)SbNMe 22

將備於二***(50毫升)的(t BuNCCNt Bu)SbCl(15.00克、45.8毫莫耳)溶液慢慢加到備於二***(100毫升)的二甲醯胺鋰(2.34克、45.8毫莫耳)冰冷懸浮液中。醯胺鋰接著溶解形成細小白色沉澱物。將反應混合物保持呈室溫且攪拌整個晚上。然後在真空下揮發溶劑、利用戊烷(100毫升)萃取灰色殘餘物、在氮氣中進行過濾(中級玻料)，及在真空下使溶劑揮發而產生深黃色油。利用分餾(120℃油浴、<50毫托耳)純化油，以於55℃時獲得澄清無色的液體。產率：12.1克、79%。1 H NMR(C6 D6 )：3.29、2.96(m,4H,CH2 CH2 )、2.87(s,6H,NMe2 )、1.25(s,18H,t -Bu)。13 C NMR(C6 D6 )：54.22(CR4 )、50.16(CH2 CH2 )、41.25(NMe2 )、31.48(CH3 )。C12 H28 N3 Sb的分析計算值：C(42.88)；H(8.40)；N(12.50)。實驗值：C(42.78)；H(8.48)；N(12.46)。A solution of ( t BuNCCN t Bu)SbCl (15.00 g, 45.8 mmol) in diethyl ether (50 ml) was slowly added to lithium dimethylamine (2.34 g, 45.8) in diethyl ether (100 ml). Millions of ice-cold suspension. Lithium amide is then dissolved to form a fine white precipitate. The reaction mixture was kept at room temperature and stirred overnight. The solvent was then evaporated in vacuo, the residue was purified eluting with pentane (100 <RTI ID=0.0></RTI><RTIgt; The oil was purified by fractional distillation (120 ° C oil bath, < 50 mTorr) to give a clear, colorless liquid at 55 °C. Yield: 12.1 g, 79%. 1 H NMR (C 6 D 6 ): 3.29, 2.96 (m, 4H, CH 2 CH 2 ), 2.87 (s, 6H, NMe 2 ), 1.25 (s, 18H, t -Bu). 13 C NMR (C 6 D 6 ): 54.22 (CR 4 ), 50.16 (CH 2 CH 2 ), 41.25 (NMe 2 ), 31.48 (CH 3 ). Analytics calculated for C 12 H 28 N 3 Sb: C (42.88); H (8.40); N (12.50). Experimental values: C (42.78); H (8.48); N (12.46).

實施例3：製備(Example 3: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)Sb(Bu)Sb( ii Pr)Pr)

將異丙基氯化鎂溶液(6.11毫升、12.21毫莫耳、2.0M備於***)慢慢加到備於二***(50毫升)的(t BuNCCNt Bu)SbCl(4.00克、12.21毫莫耳)冰***液中。如此會產生濃稠白色固體。將反應混合物加熱至室溫且攪拌整個晚上。將戊烷(50毫升)加到漿料中，及在氮氣中過濾混合物(中級玻料)。在真空下使溶劑揮發而產生淡黃色油。利用分餾(100℃油浴、<50毫托耳)純化油，以於52℃時獲得澄清無色的液體。產率：1.2克、29%。The isopropylmagnesium chloride solution (6.11 ml, 12.21 mmol, 2.0 M in diethyl ether) was slowly added to ( t BuNCCN t Bu) SbCl (4.00 g, 12.21 mmol) prepared in diethyl ether (50 ml). In an ice cold solution. This produces a thick white solid. The reaction mixture was allowed to warm to room temperature and stirred overnight. Pentane (50 ml) was added to the slurry, and the mixture was filtered under nitrogen (intermediate glass). The solvent was volatilized under vacuum to give a pale yellow oil. The oil was purified by fractional distillation (100 ° C oil bath, < 50 mTorr) to give a clear, colorless liquid at 52 °C. Yield: 1.2 g, 29%.

1 H NMR(C6 D6 )：3.18、3.00(m,4H,CH2 CH2 )、1.64(sept,1H,i Pr)、1.36(d,6H,3 J=7.5Hz,i Pr)、1.20(s,18H,t Bu)。13 C NMR(C6 D6 )：54.61(t BuC)、53.51(CH2 CH2 )、32.21(t Bu)、32.06、23.01(i PrCH)、20.23(i Pr)。C13 H29 N2 Sb的分析計算值：C(46.59)；H(8.72)；N(8.36)。實驗值：C(46.44)；H(8.73)；N(8.39)。 1 H NMR (C 6 D 6 ): 3.18, 3.00 (m, 4H, CH 2 CH 2 ), 1.64 (sept, 1H, i Pr), 1.36 (d, 6H, 3 J = 7.5 Hz, i Pr), 1.20 (s, 18H, t Bu). 13 C NMR (C 6 D 6 ): 54.61 (t BuC), 53.51 (CH 2 CH 2), 32.21 (t Bu), 32.06,23.01 (i PrCH), 20.23 (i Pr). Analysis Calculated for C 13 H 29 N 2 Sb of: C (46.59); H ( 8.72); N (8.36). Found: C (46.44); H (8.73); N (8.39).

實施例4：製備(Example 4: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)Sb(MeBu)Sb(Me 55 CC 55 ))

將備於二***(20毫升)的(t BuNCCNt Bu)SbCl(3.00克、9.16毫莫耳)溶液慢慢加到備於二***(50毫升)的五甲基環戊二烯鋰(1.30克、9.16毫莫耳)冰冷懸浮液中，以產生橘色沉澱物。將反應混合物加熱至室溫且攪拌整個晚上。然後在真空下揮發溶劑、利用戊烷(100毫升)萃取殘餘物、在氮氣中進行過濾(中級玻料)，及在真空下使溶劑揮發而產生橘色粉末。利用昇華(80℃油浴、<50毫托耳)純化固體，以得橘色結晶固體。產率：2.7克、69%。飽和二***溶液可於-37℃時取得單晶。1 H NMR(C6 D6 )：3.19、3.05(m,4H,CH2 CH2 )、2.19(s,15H,CH3 Cp)、1.18(s,18H,t -Bu)。13 C NMR(C6 D6 )：121.84(Cp)、55.38(tBuC)、54.06(CH2 CH2 )、32.45、32.14((CH3 )3 C)、12.65(CH3 Cp)。C20 H37 N2 Sb的分析計算值：C(56.22)；H(8.73)；N(6.56)。實驗值：C(56.14)；H(8.67)；N(6.39)。A solution of ( t BuNCCN t Bu)SbCl (3.00 g, 9.16 mmol) in diethyl ether (20 ml) was slowly added to lithium pentamethylcyclopentadienide (1.30) in diethyl ether (50 ml). Gram, 9.16 millimoles) in an ice-cold suspension to produce an orange precipitate. The reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was then evaporated under vacuum, the residue was taken eluted with pentane (100 mL), filtered over nitrogen (eluent), and the solvent was evaporated under vacuum to give an orange powder. The solid was purified using sublimation (80 ° C oil bath, < 50 mTorr) to give an orange crystalline solid. Yield: 2.7 g, 69%. The saturated diethyl ether solution can obtain a single crystal at -37 °C. 1 H NMR (C 6 D 6 ): 3.19, 3.05 (m, 4H, CH 2 CH 2 ), 2.19 (s, 15H, CH 3 Cp), 1.18 (s, 18H, t -Bu). 13 C NMR (C 6 D 6 ): 121.84 (Cp), 55.38 (tBuC), 54.06 (CH 2 CH 2 ), 32.45, 32.14 ((CH 3 ) 3 C), 12.65 (CH 3 Cp). Analysis Calculated for C 20 H 37 N 2 Sb of: C (56.22); H ( 8.73); N (6.56). Found: C (56.14); H (8.67); N (6.39).

實施例5：製備(Example 5: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)Sb{MeBu)Sb{Me 22 NC(NC ( ii PrN)PrN) 22 }}

將N,N’-二異丙基碳二亞胺(1.93克、2.36毫升、15.27毫莫耳)慢慢加到備於二***(50毫升)的二甲醯胺鋰(0.78克、15.27毫莫耳)的冰冷懸浮液中。所得之澄清淺黃色溶液在0℃下攪拌3小時。將備於二***(25毫升)的(t BuNCCNt Bu)SbCl(5.00克、15.27毫莫耳)溶液慢慢加到胍基鋰。添加時會產生淺黃色沉澱物。將反應混合物加熱至室溫且攪拌整個晚上。然後在真空下揮發溶劑、利用戊烷(100毫升)萃取白色殘餘物、在氮氣中進行過濾(中級玻料)，及在真空下使溶劑揮發而產生白色粉末。利用昇華(60℃油浴、<50毫托耳)純化化合物。產率：5.4克、77%。1 H NMR(C6 D6 )：4.0(vbrs,2H,i PrCH)、3.36、3.17(m,4H,CH2 CH2 )、2.53(s,6H,NMe2 )、1.41(s,18H,t -Bu)、1.34(brs,12H,i Pr)。13 C NMR(C6 D6 )：100.86(NCN)、54.83(t BuC)、50.95(CH2 CH2 )、41.85(NMe2 )、31.75(t Bu)、31.45(i PrCH)、26.17(i Pr)。C19 H42 N5 Sb的分析計算值：C(49.36)；H(9.16)；N(15.15)。實驗值：C(49.41)；H(9.34)；N(14.93)。N,N'-diisopropylcarbodiimide (1.93 g, 2.36 ml, 15.27 mmol) was slowly added to lithium dimethyl amide (0.78 g, 15.27 m) in diethyl ether (50 ml). Mohr) in an ice-cold suspension. The resulting clear pale yellow solution was stirred at 0 °C for 3 hours. A solution of ( t BuNCCN t Bu)SbCl (5.00 g, 15.27 mmol) in diethyl ether (25 ml) was slowly added to the decyl lithium. A pale yellow precipitate is produced when added. The reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was then evaporated in vacuo, the white residue was taken eluted with pentane (100 mL) The compound was purified using sublimation (60 ° C oil bath, < 50 mTorr). Yield: 5.4 g, 77%. 1 H NMR (C 6 D 6 ): 4.0 (vbrs, 2H, i PrCH), 3.36, 3.17 (m, 4H, CH 2 CH 2 ), 2.53 (s, 6H, NMe 2 ), 1.41 (s, 18H, t -Bu), 1.34 (brs, 12H, i Pr). 13 C NMR (C 6 D 6 ): 100.86 (NCN), 54.83 ( t BuC), 50.95 (CH 2 CH 2 ), 41.85 (NMe 2 ), 31.75 ( t Bu), 31.45 ( i PrCH), 26.17 ( i Pr). Analytics calculated for C 19 H 42 N 5 Sb: C (49.36); H (9.16); N (15.15). Found: C (49.41); H (9.34); N (14.93).

實施例6：製備(Example 6: Preparation ( tt BuNCHBuNCH 22 CHCH 22 NN tt Bu)Sb{CHBu)Sb{CH 33 C(C( ii PrN)PrN) 22 }}

將甲基鋰溶液(28.6毫升、45.8毫莫耳、1.6M備於已烷)慢慢加到備於二***(100毫升)的N,N’-二異丙基碳二亞胺(5.78克、45.8毫莫耳)冰***液中。所得之澄清無色溶液在0℃下攪拌3小時。將備於二***(50毫升)的(t BuNCCNt Bu)SbCl(15.0克、45.8毫莫耳)溶液慢慢加到胍基鋰。添加時會產生細小白色沉澱物，溶液相則變黃。將反應混合物加熱至室溫且攪拌整個晚上。然後在真空下揮發溶劑、利用戊烷(100毫升)萃取黃色殘餘物、在氮氣中進行過濾(中級玻料)，及在真空下使溶劑揮發而產生黃色油。使用二***(2×10毫升)和真空揮發之溶劑研磨殘餘物。如此可得黃色固體。利用昇華(70℃油浴、<50毫托耳、<-5℃冷卻劑冷指)純化化合物，以得無色結晶固體。產率：11.8克、60%。1 H NMR(C6 D6 )：3.24(m,4H,CH2 CH2 )、1.74(s,3H,CH3 CN)、1.38(s,18H,t Bu)、1.24(d,3 J=6.6Hz,i Pr)。13 C NMR(C6 D6 )：166(NCN)、54.75(CR4 )、51.12(CH2 CH2 )、31.88(i PrCH)、31.52(t Bu)、25.01(i Pr)、15.62(CH3 CN)。C18 H39 N4 Sb的分析計算值：C(49.90)；H(9.07)；N(12.93)。實驗值：C(49.73)；H(8.98)；N(12.87)。The methyllithium solution (28.6 ml, 45.8 mmol, 1.6 M in hexane) was slowly added to N,N'-diisopropylcarbodiimide (5.78 g) in diethyl ether (100 mL). , 45.8 millimoles) in ice-cold solution. The resulting clear, colorless solution was stirred at 0 °C for 3 h. A solution of ( t BuNCCN t Bu)SbCl (15.0 g, 45.8 mmol) in diethyl ether (50 ml) was slowly added to the decyllithium. When added, a fine white precipitate is produced and the solution phase turns yellow. The reaction mixture was allowed to warm to room temperature and stirred overnight. The solvent was then evaporated in vacuo, a yellow residue was taken eluted with pentane (100 mL) The residue was triturated with diethyl ether (2 x 10 mL) and solvent evaporated in vacuo. This gives a yellow solid. The compound was purified by sublimation (70 ° C oil bath, <50 mTorr, <-5 ° C coolant cold finger) to give a colorless crystalline solid. Yield: 11.8 g, 60%. 1 H NMR (C 6 D 6 ): 3.24 (m, 4H, CH 2 CH 2 ), 1.74 (s, 3H, CH 3 CN), 1.38 (s, 18H, t Bu), 1.24 (d, 3 J = 6.6 Hz, i Pr). 13 C NMR (C 6 D 6 ): 166 (NCN), 54.75 (CR 4 ), 51.12 (CH 2 CH 2 ), 31.88 ( i PrCH), 31.52 ( t Bu), 25.01 ( i Pr), 15.62 (CH) 3 CN). Analytics calculated for C 18 H 39 N 4 Sb: C (49.90); H (9.07); N (12.93). Found: C (49.73); H (8.98); N (12.87).

雖然本發明已以特定態樣、特徵結構和實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been described above in terms of specific aspects, features, and embodiments, the present invention is not intended to limit the invention, and various modifications may be made without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

第1圖Figure 1

100．．．封裝件100. . . Package

102．．．容器102. . . container

104．．．內部容積104. . . Internal volume

106．．．托盤106. . . tray

108．．．導管108. . . catheter

109．．．頸部109. . . neck

110．．．閥頭組件110. . . Valve head assembly

112．．．手動輪112. . . Manual wheel

114．．．分配埠114. . . Distribution

A、Q．．．箭頭A, Q. . . arrow

第4圖Figure 4

100．．．系統100. . . system

110．．．容器110. . . container

112、114、116、120、122、126、130、140、146．．．管線112, 114, 116, 120, 122, 126, 130, 140, 146. . . Pipeline

118．．．管線/歧管118. . . Pipeline/manifold

124．．．混合腔室124. . . Mixing chamber

128．．．蒸發器128. . . Evaporator

132．．．沉積腔室132. . . Deposition chamber

134．．．分散器134. . . Diffuser

136．．．基材136. . . Substrate

138．．．基座138. . . Pedestal

142．．．減弱單元142. . . Weakening unit

G、S、T．．．容器G, S, T. . . container

第1圖為根據一實施例之材料儲存與分配封裝件的示意圖，其含有本發明之前驅物。1 is a schematic illustration of a material storage and dispensing package containing a precursor of the present invention, in accordance with an embodiment.

第2圖為典型Sb前驅物({t BuNCH2 CH2 Nt Bu}SbNMe2 )的熱分析(STA)圖。Figure 2 is a thermal analysis (STA) plot of a typical Sb precursor ({ t BuNCH 2 CH 2 N t Bu}SbNMe 2 ).

第3圖為{t BuNCH2 CH2 Nt Bu}SbNMe2 的1 H和13 NMR圖譜。Figure 3 is a 1 H and 13 NMR spectrum of { t BuNCH 2 CH 2 N t Bu}SbNMe 2 .

第4圖為根據本發明一實施例之氣相沉積系統的示意圖，其中添加抗預反應劑至氣相沉積系統內的一或多個進料流，可抑制前驅物預先反應。4 is a schematic illustration of a vapor deposition system in accordance with an embodiment of the present invention in which the addition of a pre-reactant to one or more feed streams in a vapor deposition system inhibits pre-reaction of the precursor.

Claims (25)

一種銻前驅物，具有下列分類I的化學式之一： 其中：R、R1 、R2 、R3 、R4 、R5 、R6 、R7 、R8 和R9 彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基和乙醯烷基；X彼此為相同或不同，且個別選自氫基(H)、鹵素、C1 -C6 烷基、C1 -C6 烷氧基、C3 -C8 環烷基、C6 -C10 芳基、矽烷基、取代矽烷基、醯胺基、胺基烷基、烷基胺、烷氧烷基、芳氧烷基、亞胺烷基、乙醯烷基、脒基(amidinate)、脈基(guanidinate)、異尿酸鹽(isourate)和環戊二烯基(C5 R5 )；以及n為1-7之一整數。A ruthenium precursor having one of the following chemical formulas of classification I: Wherein: R, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 are the same or different from each other, and are each selected from the group consisting of hydrogen (H), halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkyl An amine, an alkoxyalkyl group, an aryloxyalkyl group, an imidoalkyl group, and an ethoxyalkyl group; X are the same or different from each other, and are each selected from the group consisting of a hydrogen group (H), a halogen, a C 1 -C 6 alkyl group, and a C group. 1- C 6 alkoxy, C 3 -C 8 cycloalkyl, C 6 -C 10 aryl, decyl, substituted decyl, decyl, aminoalkyl, alkylamine, alkoxyalkyl, Aryloxyalkyl, imidoalkyl, ethoxyalkyl, amidinate, guanidinate, isourate, and cyclopentadienyl (C 5 R 5 ); and n is 1 -7 an integer. 如申請專利範圍第1項所述之銻前驅物，選自下列化合物之一： The precursor of the ruthenium as described in claim 1 of the patent application is selected from one of the following compounds: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 如申請專利範圍第1項所述之銻前驅物，包含一具以下化學式的雙醯胺銻： The ruthenium precursor as described in claim 1 of the patent application, comprising a bisguanamine hydrazine having the following chemical formula: 一種組成物，包含：(a)如申請專利範圍第1-9項任一項所述之一銻前驅物；以及(b)一溶劑介質，該化合物係溶解在該溶劑介質中。 A composition comprising: (a) one of the ruthenium precursors according to any one of claims 1 to 9; and (b) a solvent medium dissolved in the solvent medium. 如申請專利範圍第10項所述之組成物，其中該溶劑介質包含一碳氫化合物溶劑。 The composition of claim 10, wherein the solvent medium comprises a hydrocarbon solvent. 如申請專利範圍第11項所述之組成物，其中該碳氫化合物溶劑包含烷烴、芳香羥和胺的一或多者。 The composition of claim 11, wherein the hydrocarbon solvent comprises one or more of an alkane, an aromatic hydroxy group, and an amine. 如申請專利範圍第1項所述之銻前驅物，其中n為1-6之一整數。 The ruthenium precursor as described in claim 1 wherein n is an integer of 1-6. 如申請專利範圍第11項所述之組成物，其中該碳氫化合物溶劑包含己烷、庚烷、辛烷、戊烷、苯、甲苯、三乙胺和三級丁胺的一或多者。 The composition of claim 11, wherein the hydrocarbon solvent comprises one or more of hexane, heptane, octane, pentane, benzene, toluene, triethylamine, and tertiary butylamine. 一種前驅物蒸氣，包含如申請專利範圍第1-9項任 一項所述之一銻前驅物的一蒸氣。 A precursor vapor comprising any of items 1-9 of the scope of the patent application One of the vapors of one of the precursors. 如申請專利範圍第15項所述之前驅物蒸氣，更包含一共反應物，選自由氧氣(O2 )、一氧化二氮(N2 O)、水(H2 O)、臭氧、氧氣(O2 )電漿、氫氣、氫氣(H2 )/電漿、胺、亞胺、肼、矽烷、鍺烷、氨氣、烷烴、烯烴、炔烴、硼烷和其相容混合物所組成之一群組，其中該前驅物蒸氣同時伴隨該共反應物輸送，或者該前驅物蒸氣以一脈衝方式而其中該前驅物蒸氣與該共反應物為暫時地分開。The precursor vapor as described in claim 15 of the patent application further comprises a total of reactants selected from the group consisting of oxygen (O 2 ), nitrous oxide (N 2 O), water (H 2 O), ozone, and oxygen (O). 2 ) a group of plasma, hydrogen, hydrogen (H 2 ) / plasma, amine, imine, hydrazine, decane, decane, ammonia, alkanes, alkenes, alkynes, borane and compatible mixtures thereof a set wherein the precursor vapor is simultaneously accompanied by the co-reactant transport, or the precursor vapor is in a pulsed manner wherein the precursor vapor is temporarily separated from the co-reactant. 一種沉積一含銻膜至一基材上的方法，該方法包含揮發如申請專利範圍第1-9項任一項所述之一銻前驅物以產生一前驅物蒸氣、以及在一沉積條件下，使該基材接觸該前驅物蒸氣而形成該含銻膜於該基材上。 A method of depositing a ruthenium-containing film onto a substrate, the method comprising volatilizing a ruthenium precursor according to any one of claims 1 to 9 to produce a precursor vapor, and under a deposition condition The substrate is contacted with the precursor vapor to form the ruthenium containing film on the substrate. 一種形成一鍺銻碲(GST)膜至一基材上的方法，該方法包含利用得自如申請專利範圍第1-9項任一項所述之一銻前驅物的一蒸氣來沉積銻於該基材上。 A method of forming a ruthenium (GST) film onto a substrate, the method comprising depositing a ruthenium using a vapor obtained from a ruthenium precursor according to any one of claims 1-9 On the substrate. 一種製造一相變隨機存取記憶體(PCRAM)裝置的方法，該方法包含形成一鍺銻碲(GST)膜至用於製造該裝置的一基材上，其中該形成步驟包含利用得自如申請專利範圍第1-9項任一項所述之一銻前驅物的一蒸氣來沉積銻於該基材上。 A method of fabricating a phase change random access memory (PCRAM) device, the method comprising forming a germanium (GST) film onto a substrate for fabricating the device, wherein the forming step comprises utilizing a free application A vapor of the ruthenium precursor of any one of the items 1-9 of the patent is deposited on the substrate. 一種形成一含銻膜至一基材上的方法，該方法包含揮發如申請專利範圍第1-9項任一項所述之一銻前驅物以產生一前驅物蒸氣、以及在一原子層沉積條件或一化學氣相沉積條件下，使該前驅物蒸氣接觸該基材。 A method of forming a ruthenium-containing film onto a substrate, the method comprising volatilizing a ruthenium precursor according to any one of claims 1 to 9 to produce a precursor vapor, and depositing in an atomic layer The precursor vapor is contacted to the substrate under conditions or a chemical vapor deposition condition. 如申請專利範圍第20項所述之方法，其中該含銻膜為一鍺銻碲(GST)膜。 The method of claim 20, wherein the ruthenium-containing film is a ruthenium (GST) film. 如申請專利範圍第20項所述之方法，其中該含銻膜為一無定形鍺碲(GeTe)膜。 The method of claim 20, wherein the ruthenium-containing film is an amorphous germanium (GeTe) film. 如申請專利範圍第20項所述之方法，其中該含銻膜為一無定形銻碲(SbTe)膜。 The method of claim 20, wherein the ruthenium-containing film is an amorphous bismuth (SbTe) film. 如申請專利範圍第20項所述之方法，包含進行一相變隨機存取記憶體製造製程。 The method of claim 20, comprising performing a phase change random access memory manufacturing process. 一種對抗得自如申請專利範圍第1-9項任一項所述之一銻前驅物的一氣相前驅物在接觸一基材而用以沉積一膜成分於該基材上時產生預先反應的方法，該方法包含在該基材接觸該氣相前驅物前，先使該基材接觸一抗預反應劑，該抗預反應劑選自由(i)一異質原子(O、N、S)有機路易士(Lewis)鹼化合物、(ii)一自由基抑制劑和 (iii)一含氘試劑組成之一群組。A method for producing a pre-reaction when a gas phase precursor of a ruthenium precursor according to any one of claims 1 to 9 is contacted with a substrate for depositing a film component on the substrate The method comprises contacting the substrate with a primary anti-reactant selected from (i) a heteroatom (O, N, S) organic Lewis prior to contacting the substrate with the vapor precursor. Lewis base compound, (ii) a free radical inhibitor and (iii) a group of quinone-containing reagents.
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